Lactamic polymer containing an acetoacetate moiety

ABSTRACT

The invention provides lactamic polymers comprising an acetoacetate moiety. The lactamic polymers may be readily functionalized and the functionalized lactamic polymers may be further derivatized to provide a wide variety of useful polymers having desirable chemical and physical properties. The lactamic polymers of the invention may be employed in a wide variety of compositions. (A); (B) wherein R 1 -R 6 , w, x, y, z, and n are described herein.

FIELD OF THE INVENTION

The invention provides lactamic polymers comprising an acetoacetatemoiety. The lactamic polymers may be readily functionalized and thefunctionalized lactamic polymers may be further derivatized to provide awide variety of useful polymers having desirable chemical and physicalproperties. The lactamic polymers of the invention may be employed in awide variety of compositions.

BACKGROUND OF THE INVENTION

Inkjet printers form an image by firing a plurality of discrete drops ofink from one or more nozzles on to the surface of a recording sheetplaced adjacent the nozzles. Modern inkjet printers can print on almostany conventional paper or similar medium. The quality of images producedby such printers is greatly affected by the properties of the mediumused. More particularly, to produce high quality images reliably, it isnecessary that the recording medium, i.e., the inkjet recording sheet,dry rapidly, exhibit good ink adhesion, resist image cracking, notpromote excessive spreading of the ink droplet, not promote “wicking”,that is spreading of ink by capillary action through fibrous medium suchas paper, and, importantly, be such that the contrast of the dried imagewith moist surfaces does not result in bleeding of ink from the image.Printing technologies are applied to many different surfaces, forexample, polyester film, polyolefin films including polyethylene (PE),polypropylene (PP), polycarbonate, polyimide films, metals (i.e.,aluminum, steel, copper), glass, vinyl film, Tyvek, canvas,polyvinylidene chloride films, textiles, canvas, leather, rubber, paper,polyurethane, ceramics, wood and the like.

In curable ink systems, the inks can be prepared by a polymerizationprocess initiated by thermal or photo irradiation (α, γ, and x-rays, UV,E-beam, and the like). Desirable properties in polymeric inks includesolution viscosity, lubricity, gloss, cure speed, adhesion, impactresistance, toughness, coating hardness, water resistance, tack, surfacetension, wetting, foaming, tensile strength, solvency, dispersiveproperties, flexibility, chemical resistance, abrasion resistance, andpenetration.

The functional attributes of acetoacetoxyethyl methacrylate aredisclosed in Eastman Chemical's “Acetoacetoxyethyl methacrylate (AAEM)Acetoacetyl Chemistry” Brochure (Publication Number N-319C, December1999), which disclosure is incorporated by reference herein. Thefunctional and chemical attributes of diketene chemistry are disclosedin “Diketene” by R. Clemens (Chemical Reviews, Volume 86, Number 2,April 1986), which disclosure is incorporated by reference herein. Thefunctional and chemical attributes of ketene chemistry are disclosed in“Ketenes II” by T Tidwell (J. Wiley and Sons, New Jersey, USA, 2006),which disclosure is incorporated by reference herein.

EP 1578824B1 describes a curable liquid composition containing anacryloyl group containing resin produced by reacting monofunctionalvinyl compounds and multifunctional acrylic esters with β-dicarbonylgroup containing compound in which the two activated hydrogen atoms arein its methylene position. Self-initiating photocurable resins thatUV-cure with little or no photoinitiator are described in Michael L.Gould et al., Novel Self-Initiating UV-Curable Resins: Generation Three,1 PROCEEDINGS FROM RADTECH EUROPE 05, 245-51 (2005). These disclosuresare incorporated by reference herein.

U.S. 2010/0041846 discloses lac tam/vinyl alcohol copolymers,specifically, hydrophobic cross-linkable) acetylated lactam/vinylalcohol copolymers. U.S. Pat. No. 6,933,024 discloses the use andpreparation of poly(vinylpyrrolidone-(PVP) co-vinylalcohol) as an inkjetrecording material by hydrolyzing PVP/polyvinylacetate copolymer. U.S.Pat. No. 4,350,788 describes a synthetic resin emulsion containing anacetoacetylated polyvinyl alcohol. U.S. Pat. No. 2,536,980 describessynthetic polyvinyl alcohol-1-butene-1,3-diones. U.S. Pat. No. 5,227,423describes latex paint comprised of polymers having anon-self-polymerizable monomer, such as maleic acid and itaconic acid, aco-polymerizable monomer, such as a N-vinyl lactam, an acrylate, such as2-hydroxyethyl acrylate, a wet adhesion promoting monomer, such asacetoacetoxyethyl methacrylate.

Additional examples for lactamic monomers can be found in “A novel routeto substituted poly(vinyl pyrrolidone)s via simple functionalization of1-vinyl-2-pyrrolidone in the 3-position by ring-opening reactions” by H.Reinecke et. al. (Eur. Poly. J., 46 (2010) p 1557-1562. Additionalexamples for lactamic monomers can be found in “Synthesis andpolymerization of new pyrrolidone-containing methacrylate monomers” byT. P. Davis et. al. (Polymer, 39, 17, p 4165-4169, 1998).

Lactamic polymers, such as polyvinyl pyrrolidone (PVP), are well knownto exhibit a high degree of functional utility; particularly in inks andgraphic art coatings. One challenge with lactamic polymers is watersolubility and water sensitivity. As printing technology evolves, thereis a need for new functional materials that incorporate facile methodsfor achieving water resistance improvements.

Accordingly, new polymeric inks are desirable having improved propertiesincluding solution viscosity, lubricity, gloss, cure speed, adhesion,impact resistance, toughness, coating hardness, water resistance,pigment surface decoration, tack, surface tension, wetting, foaming,tensile strength, solvency, dispersive properties, flexibility, chemicalresistance, abrasion resistance, and penetration.

SUMMARY OF THE INVENTION

The invention provides lactamic polymers comprising an acetoacetatemoiety having the following structure:

wherein each R₁ and R₂ are independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; w, x, y, and z are molepercent, the sum of which=100%, with the proviso that z may be 0% molepercent; and each n is an integer independently ranging from 1-4.

The invention further provides lactamic polymers comprising anacetoacetate moiety having the following structure:

wherein each R₁ and R₂ are independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; x, y, and z are molepercent, the sum of which=100%, with the proviso that z may be 0% molepercent; and each n is an integer independently ranging from 1-4.

The invention further provides functionalized lactamic polymers having astructure selected from the group consisting of:

wherein w, x, and y are mole percent, the sum of which=100%.

The invention further provides lactamic polymers having a structureselected from the group consisting of:

wherein w, x, and y are mole percent, the sum of which=100%.

The invention further provides a functionalized lactamic polymer havinga structure selected from the group consisting of:

wherein x and y are mole percent, the sum of which=100%; and n is aninteger independently ranging from 1-4.

The lactamic polymers of the invention may be employed in a wide varietyof compositions.

DETAILED DESCRIPTION

The invention provides lactamic polymers containing an acetoacetatemoiety. The lactamic polymers may be readily functionalized and thefunctionalized lactamic polymers may be further derivatized to provide awide variety of useful polymers having desirable chemical and physicalproperties. In one aspect, the lactamic polymers comprise a lactamicmonomer, a maleic anhydride derived monomer, a monomer containing anacetoacetate moiety, and optionally a monomer to provide desirablecharacteristics in the polymer for use in a wide variety ofcompositions. In another aspect, the lactamic polymers comprise alactamic monomer, a monomer containing an acetoacetate moiety, andoptionally a monomer to provide desirable characteristics in the polymerfor use in a wide variety of compositions. The polymers may be random,blocked, or alternating polymers.

Lactams, such as poly(vinylpyrrolidone) (PVP), are water-solubleamphiphilic nontoxic polymers commonly used in a wide range ofapplications in the pharmaceutical and nutritional areas, as well as incosmetics, personal hygiene, membranes, paintings, surfactants,dispersions, adhesives, inks, and the like. However, many lactams lackreactive groups that limit the possibility of adding new functionalgroups to the polymer to modify their physical and chemical properties,and thus their usefulness in compositions.

The maleic anhydride derived monomers may be partially or fullyring-opened to provide amic acids, carboxylic acids, carboxylic acidicsalts, imides, esters, and mixtures thereof. The partially or fullyring-opened maleic anhydride derived monomers may be employed to varythe hydrophilic/hydrophobic character of the lactamic polymers. Themonomer containing an acetoacetate moiety in the polymer provides amonomer that can be functionalized with a wide variety of groups tochange the physical and chemical properties of the polymer. The optionalmonomer can further provide additional desirable characteristics in thepolymer. The invention overcomes many of these problems by providing theability to add a wide variety of functional groups to lactamic polymersand further to provide the ability to radically polymerize thesubstituted lactamic polymers. The lactamic polymers may be employed assolids, in solvents, and in reactive solvents.

In another aspect, application of a wide variety of compositionscomprising the novel modified polymers are provided, includingadhesives, aerosols, agricultural compositions, anti-soil redepositionagents, batteries, beverages, biocides, block copolymers, branchedcopolymers, cementing compositions, cleaning compositions, coatingcompositions, conductive materials, comb copolymers, cosmeticcompositions, cross-linkers, decorated pigment surfaces, dentalcompositions, detergents, dispersants, drugs, electronics,encapsulations, foods, graft copolymers, hair sprays,household-industrial-institutional (HI&I), inks and coatings (suitablefor use as a moisture resistant inkjet recording medium), interlaminateadhesives, lithographic solutions, membrane additive compositions, metalworking fluids, oilfield compositions, paints, paper, personal carecompositions, pharmaceuticals, pigment additives, plasters, plastics,printing, reactive biocides, refractive index modifiers, sequestrants,soil release compositions, static control agents, and wood-carecompositions.

Personal care compositions refers to such illustrative non-limitingcompositions as cosmetics, drug delivery systems, hair, oil,pharmaceuticals, pigment dispersions, preservative compositions,including those to alter the color and appearance of the skin, skin,sun, and tissue regeneration scaffolds. Other personal care compositionsinclude, but are not limited to, modified natural oils for increasedflexibility in styling, durable styling, increased humidity resistancefor hair, skin, and color cosmetics, sun care water-proof/resistance,wear-resistance, shower gels, shampoos, and thermal protecting/enhancingcompositions. Dental personal care compositions include dentureadhesives, toothpastes, mouth washes, and the like. Pharmaceuticalcompositions include tablet coatings, tablet binders, transdermalpatches, and the like. The wide variety of compositions are describedbelow in detail.

As used herein, the following terms have the meanings set out below.

The term “acetoacetate moiety” refers to the group

wherein R¹ is defined herein. The CH₃—CO— moiety in the acetoacetatemoiety is thermally and photically labile.

The term “acidic conditions” refers to conditions relating to the pHvalue of an aqueous solution. Pure water is considered to be neutral,with a pH close to 7.0 at 25° C. Solutions with a pH value less than 7are considered to be acidic solutions.

The term “basic conditions” refers to conditions relating to the pHvalue. Pure water is considered to be neutral, with a pH close to 7.0 at25° C. Solutions with a pH value greater than 7 are considered to bebasic or alkaline.

The term “branched and unbranched alkyl groups” refers to alkyl groups,which may be straight chained or branched. For example, the alkyl groupshave from 1 to about 18 carbon atoms, more particularly, from 1 to about10 carbon atoms, and yet more particularly from 1 to about 6 carbonatoms. Branched groups include isopropyl, tert-butyl, and the like.

The term “condensation reaction” refers to a chemical reaction in whichtwo molecules or moieties (functional groups) combine to form one singlemolecule, together with the loss of a small molecule. When this smallmolecule is water, the reaction is known as a dehydration reaction.

The term “copolymer” refers to chains comprising more than one type ofmonomer unit.

The term “halogen” refers to chloro, bromo, iodo and fluoro, and in oneembodiment is bromo and/or chloro.

The term “heteroatom” refers to atoms such as oxygen, nitrogen, sulfur,and phosphorous. When the heteroatom is a nitrogen atom, the nitrogenatom may be present in the form of a quaternary amine.

The term “hydrolyzing” refers to a hydrolysis reaction (hydrolysis) inwhich a parent molecule is split into two parts by the addition of amolecule of water. During the hydrolysis reaction, molecules of waterare split into hydrogen cations (H⁺) and hydroxide anions (OH⁻). Onefragment of the parent molecule gains a hydrogen cation from the watermolecule; the other fragment gains the hydroxide anion.

The term “imide” refers to an organic compound comprising two carbonylgroups (acyl groups) bound to nitrogen atom. The nitrogen atom in theimide functional group may or may not be substituted with an organicfunctional group.

The term “inert solvent” refers to a solvent that does not interferechemically with the reaction.

The term “intermediate compound” refers to a compound, which is producedduring the course of a chemical synthesis. An intermediate compound isnot itself, the final product, but is used in further reactions, whichproduce the final product. This is in contrast to the starting materialand final product. An intermediate compound is generally not isolated orpurified but rather is used “as is” in the synthesis. Many differentintermediate compounds may be produced during the course of a synthesis,especially for economical reasons on the industrial level.

The term “lactam” refers to a cyclic amide, which generally can containfrom 4-7 ring atoms in total.

The term “maleic anhydride” (cis-butenedioic anhydride, toxilicanhydride, 2,5-dioxofuran) is an organic compound with the formulaC₂H₂(CO)₂O. Maleic anhydride is the acid anhydride of maleic acid and inits pure state it is a colorless or white solid with an acrid odor.Maleic anhydride has the structure:

The term “maleimide” is the chemical compound with the formulaH₂C₂(CO)₂NH. Maleimide is an unsaturated imide, which is an importantbuilding block in organic synthesis. The name is a contraction of maleicacid and imide, the —C(O)NHC(O) functional group. Maleimide has thestructure:

The term “Michael addition” or “Michael reaction” generally refers tothe nucleophilic addition of a carbanion or another nucleophile to analpha, beta unsaturated carbonyl compound (electrophile).

The term “mineral acid” refers to an acid derived from one or moreinorganic compounds. Mineral acids release hydrogen ions when dissolvedin water. Commonly used mineral acids are sulfuric acid, hydrochloricacid, and nitric acid.

The term “monomer” refers to the repeat units comprising a polymer. Amonomer is a small molecule that chemically bonds to other monomers toform a polymer.

The term “non-homopolymer” refers to a polymer formed from two or moremonomers and includes essentially all polymers that are nothomopolymers. Nonlimiting examples of non-homopolymers includecopolymers, terpolymers, tetramers, and the like, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

The term “oligomer” refers to a polymer molecule consisting of only afew monomeric units that are connected by covalent bond. For example,dimers, trimers, tetramers, etc. The term “polymer” refers to a largemolecule (macromolecule) composed of repeating structural units(monomers) connected by covalent chemical bonds. The terms oligomer andpolymer are used interchangeably herein.

The term “pH” refers to a measure of the acidity or basicity of anaqueous solution. Pure water is considered to be neutral, with a pHclose to 7.0 at 25° C. Solutions with a pH less than 7 are considered tobe acidic and solutions with a pH greater than 7 are considered to bebasic or alkaline.

The term “pharmaceutically acceptable,” such as pharmaceuticallyacceptable carrier, excipient, etc., means pharmacologically acceptableand substantially non-toxic to the subject to which the particularcompound is administered.

The term “pharmaceutically acceptable salt” refers to conventionalacid-addition salts or base-addition salts that retain the biologicaleffectiveness and properties of the compounds and are formed fromsuitable non-toxic organic or inorganic acids or organic or inorganicbases. Sample acid-addition salts include those derived from inorganicacids such as hydrochloric acid, hydrobromic acid, hydroiodic acid,sulfuric acid, sulfamic acid, phosphoric acid and nitric acid, and thosederived from organic acids such as p-toluenesulfonic acid, salicylicacid, methanesulfonic acid, oxalic acid, succinic acid, citric acid,malic acid, lactic acid, fumaric acid, and the like. Samplebase-addition salts include those derived from ammonium, potassium,sodium, and quaternary ammonium hydroxides, such as for example,tetramethylammonium hydroxide. Chemical modification of a pharmaceuticalcompound (i.e., drug) into a salt is a technique well known topharmaceutical chemists to obtain improved physical and chemicalstability, hydroscopicity, and solubility of compounds. See, e.g., H.Ansel et. al., Pharmaceutical Dosage Forms and Drug Delivery Systems(6^(th) Ed. 1995) at pp. 196 and 1456-1457.

The term “polymerization” refers to methods for chemically reactingmonomer compounds to form polymer chains. The polymer chain may bealternating, blocked, or random. The type of polymerization method maybe selected from a wide variety of methods. Such methods include, butare not limited to, free radical polymerization methods, such asclassical radical polymerization and controlled radical polymerization,Nitroxide Mediation Polymerization (NMP), Atom Transfer RadicalPolymerization (ATRP), and Reversible Addition FragmentationChain-Transfer (RAFT).

The term “respectively” is a term that denotes that the items in a listcorrespond to each other in the order they are given. With reference totwo or more items, the term refers in a parallel or sequential manner.

The invention provides lactamic polymers comprising an acetoacetatemoiety having the following structure:

wherein each R₁ and R₂ are independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; w, x, y, and z are molepercent, the sum of which=100%, with the proviso that z may be 0% molepercent; and each n is an integer independently ranging from 1-4.

In one aspect, each R₁ and R₂ are independently hydrogen or methyl; R₃is —C(O)OCH₂CH₂—; each R₄ is independently selected from the groupconsisting of functionalized and unfunctionalized alkoxy, amide, aryl,carbonyl, carboxyl, cycloalkyl groups, and moieties derived fromtriethoxyvinyl silane, wherein any of the before mentioned groups may bewith or without heteroatoms, and mixtures thereof; each R₅ isindependently selected from the group consisting of C₁-C₈ functionalizedand unfunctionalized alkyl and alkenyl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof. w may range from 1-97%, x may range from 1-97%, y may rangefrom 1-97%, and z may range from 0-96%; more particularly, w may rangefrom 1-60%, x may range from 1-60%, y may range from 1-60%, and z mayrange from 0-80%; most particularly, w may range from 1-50%, x may rangefrom 1-50%, y may range from 1-50%, and z may range from 0-80%; and nmay range from 1-3.

In one aspect, the polymer has a structure selected from the groupconsisting of:

The invention further provides lactamic polymers comprising anacetoacetate moiety having the following structure:

wherein each R₁ and R₂ are independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; x, y, and z are molepercent, the sum of which=100%, with the proviso that z may be 0% molepercent; and each n is an integer independently ranging from 1-4.

In one aspect, each R₁ and R₂ are independently hydrogen or methyl; R₃is —C(O)OCH₂CH₂—; each R₄ is independently selected from the groupconsisting of functionalized and unfunctionalized alkoxy, amide, aryl,carbonyl, carboxyl, cycloalkyl groups, and moieties derived fromtriethoxyvinyl silane, wherein any of the before mentioned groups may bewith or without heteroatoms, and mixtures thereof; each R₅ isindependently selected from the group consisting of C₁-C₈ functionalizedand unfunctionalized alkyl and alkenyl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof. x may range from 1-98%, y may range from 1-98%, and z may rangefrom 0-97%; more particularly, x may range from 1-95%, y may range from1-40%, and z may range from 0-80%; most particularly, x may range from1-70%, y may range from 1-30%, and z may range from 0-50%; and n mayrange from 1-3.

In one aspect, the polymer has a structure selected from the groupconsisting of:

The invention further provides functionalized lactamic polymers having astructure selected from the group consisting of:

wherein w, x, and y are mole percent, the sum of which=100%.

The invention further provides lactamic polymers having a structureselected from the group consisting of:

wherein w, x, and y are mole percent, the sum of which=100%.

The invention further provides a functionalized lactamic polymer havinga structure selected from the group consisting of:

wherein x and y are mole percent, the sum of which=100%; and n is aninteger independently ranging from 1-4.

The acetyl group (CH₃CO—) present in the monomer containing anacetoacetate moiety is thermally and photically labile. Upon heating orexposure to light, this group can decompose, resulting in the formationof a radical that can form “macro-initiator” or “self-initiator”polymers. The resulting polymers may require no or very little photic orheat initiators, depending upon the particular lactamic polymer. The“macro-initiator” lactamic polymers may then be reacted via apolymerization reaction with a variety of monomer moieties comprising afunctional group capable of “addition polymerization” as a result ofexposure to a free radical. Examples of suitable “additionpolymerizable” monomers include styrenics, vinylics, acrylates, maleics,maleimides, dienes, etc. Insight to addition polymerization processesand techniques can be found in “Principles of Polymer Chemistry” by PaulJ. Flory (Cornell University Press, Ithica, N.Y., 1953), whichdisclosure is incorporated by reference herein. Further insight can alsobe found in “Principles of Polymerization, 4^(th) Ed.” by George Odian(J. Wiley and Sons, Hoboken, N.J., 2004), which disclosure isincorporated by reference herein. Properties of many useful monomers canbe found in the “Polymer Handbook, 4^(th) Ed.,” edited by J. Brandrupet. al. (J. Wiley and Sons, New York, 1999), which disclosure isincorporated by reference herein.

The acetoacetate function is also suitable for reaction numerous otherchemical moieties. These include aldehydes, including formaldehyde andglyoxal, diazonium salts, isocyanates including hexylene diisocyanate,and the like. Further moieties suitable for derivatization include thosedisclosed in Eastman brochure Publication N-319C, December 1999 entitled“Acetoacetoxyethyl Methacrylate (AAEM) Acetoacetyl Chemistry, whichdisclosure is incorporated by reference herein.

In addition to acetoacetoxyethyl methacrylates, other suitableapproaches to forming the requisite acetoacetate functionality includemay be employed including diketene, t-butylacetoacetate (esterexchange), acetoacetamides, and the like.

The invention also provides methods for preparing the macro-initiatorlactamic polymers containing an acetoacetate moiety. The macro-initiatorlactamic polymers can be prepared by Michael Addition of an acetoacetateto an acrylate. For example, when a “Michael Addition” is carried out onthe following acetoacetate and acrylate, the following lactamic polymerscontaining an acetoacetate moiety may be prepared.

In this example, a strong base is employed to deprotonate theacetoacetate methylene group. The resulting carbon anion nucleophileattacks the acrylate, resulting in the formation of a new carbon-carbonbond. The integers x, y, and z correspond to the number of units of eachmonomer in the original polymer. The resulting acetoacetate moiety isthermally and photically labile and, upon heating or exposure to lighthis acetoacetate moiety can decompose resulting in the loss of theacetyl group (CH₃CO—) and formation of a lactamic polymeric radical. Thelactamic polymeric radical is a “macro-initiator” capable of initiatingpolymerization with a free radical polymerizable monomer. This reactioncan quantitatively utilize the acetoacetate or can yield excessacetoacetate.

For example, when butyl acrylate is treated with the “macro-initiator”product(s) above, the resulting polymer(s) formed may be a blockcopolymer comprising a lactamic macro-initiator “block” and a butyl(meth)acrylate “block.”

The integer A corresponds to the number of units of each free radicalpolymerizable monomer in the polymer formed from reaction with themacro-initiator. The reverse reaction is also possible, where anacetoacetate functional polymer can also be “block” functionalized witha lactamic monomer as well. Where an acrylate based acetoacetatefunctional polymer is made “lactamic” by macro-initiation of a lactamicmonomer.

The optional monomer can include hydroxyethyl acrylate (HEA),hydroxyethyl methacrylate (HEMA), hydroxybutyl acrylate (HBA), ethylhexyl methacrylate (EHMA), phenoxy ethyl acrylate (PEA), vinylenecarbonate, hydroxyethyl pyrrolidone methacrylate, vinyl acetate (VA),ethyl acrylate, methyl acrylate, isobutyl (meth)acrylates,methylmethacrylate, dimethylaminoethyl methacrylate (DMAEMA),dimethylaminopropyl methacrylamide (DMAPMA), acrylamide, methacrylamide,acrylonitrile, isobornyl acrylate, cyanoacrylates, C8-C10 acrylate(ODA), ethylene, styrene, C₈-C₁₀ acrylate, highly branched vinyl ester,maleic anhydride (MAN), acrylic acid (AA), sodium vinylsulfonate,diacetone acrylamide, vinyl carbonate, mono-acrylated glycols and glycolethers, vinyl ethylene carbonate, vinyl chloride, 4-vinyl aniline,vinylpyridine, trimethylvinylsilane, glycidyl acrylate, vinylpropionate, vinyl ethers, crotonic acid, polyfunctional acrylates,polyfunctional allyl ethers, N-vinyl imidazole, glycidyl methacrylate(GMA) and allyl acetate and allyl alcohol.

The invention discloses reactive co-solvents. These materials consist of(meth)acryl monomers or pre-polymers, a (meth)acryl ester of an epoxytype monomer or pre-polymer, and a urethane type monomers orpre-polymers.

Examples of reactive co-solvents include but are not limited to2-hydroxy methyl methacrylate (HEMA), 2-hydroxy ethyl acrylate (HEA),2-phenoxy ethyl acrylate (PEA), 2-ethylhexyl-diglycol acrylate,2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA), lauryl acrylate (LA), Stearylacrylate (SA), isobornyl acrylate (IBOA), acrylic acid-2-ethylhexylester, isodecyl acrylate, diacetone acrylamide, acryloyl morpholine(ACMO), cyclic trimethylolpropane formal acrylate (CTFA),3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC),4-hydroxybutyl acrylate, (3-Acrylamidopropyl)trimethylammonium chloride(APTAC), C8-C10 acrylate (ODA), isodecyl acrylate (ISODA), laurylmethacrylate (LM), stearyl methacrylate (SM), 2,2,2-Trifluoroethylmethacrylate, 2-Acrylamido-2-methyl-1-propanesulfonic acid,2-Acrylamido-2-methyl-1-propanesulfonic acid sodium salt,[2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide,[3-(Methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxideinner salt, 1,6-hexanediol diacrylate (HDDA), dipropylene glycoldiacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), water,alcohol, hydro-alcohol mixtures, 1,4-butanediol diacrylate (BDDA),Tripropylene glycol diacrylate (TPGDA), dipropyleneglycol diacrylate(DPGDA), Tripropylene glycol diacrylate (TRPGDA), 1,9-nonanedioldiacrylate (NNDA), neopentyl glycol diacrylate (NPGDA), propoxylatedneopentyl glycol diacrylate (NPG2PODA), polyethylene glycol (200)diacrylate (PEG(200)DA), polyethylene glycol (400) diacrylate(PEG(400)DA), polyethylene glycol (600) diacrylate (PEG(600)DA),ethoxylated bisphenol-A diacrylate (BPA2EODA), triethylene glycoldiacrylate (TEGDA), triethylene glycol dimethacrylate (TEGDMA), glycerolpropoxylated triacrylate (GPTA), diethylene glycol dimethacrylate(DEGDMA), ethoxylated bisphenol-A dimethacrylate (BPA10EODMA),trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate(PET3A), ethoxylated trimethylolpropane triacrylate (TMP3EOTA),propoxylated tri-methylolpropane triacrylate (TMP3POTA), propoxylatedglyceryl triacrylate (GPTA), trimethylolpropane trimethylacrylate(TMPTMA), ethoxylated trimethylolpropane trimethacrylate (TMP3EOTMA),2,2-dionol diacrylate, pentaerythritol tetraacrylate (PETA),neopentylglycol diacrylate hydroxypivalate, 2-acryloyloxyethylphthalicacid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid,dimethyloltricyclodecane diacrylate, 2-acryloyloxyethylsuccinic acid,nonylphenol ethylene oxide adduct acrylate, phenol acrylates,methoxy-polyethylene glycol acrylate, tetramethylolmethane triacrylate,dipentaerythritol hexaacrylate (DPHA), isocyanate-functional unsaturatedacrylic ester resin, urethane diacrylates oligomers, urethane acrylates,modified urethane acrylates, polyester acrylates, modified bisphenol Adiacrylate, phenoxy-polyethylene glycol acrylate, bisphenol A propyleneoxide modified diacrylate, bisphenol A ethylene oxide adduct diacrylate,pentaerythritol triacrylate hexamethylenediisocyanate, urethaneprepolymer, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate,carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate,glycidyl acrylates, acrylamides, polyfunctional acrylamides,polyfunctional (polyethylene glycol) acrylates, polyfunctional vinylamides, 1,4-butane-diol-monoacrylate and/or diglycidyl ether of1,4-butanediol, and the like. Mixtures of monomers are also envisionedin the invention.

Additional examples include methyl vinylether, ethyl vinylether, propylvinylether, n-butyl vinylether, t-butyl vinylether, 2-ethylhexylvinylether, n-nonyl vinylether, lauryl vinylether, cyclohexylvinylether, cyclohexylmethyl vinylether, 4-methylcyclohexylmethylvinylether, benzyl vinylether, dicyclopentenyl vinylether,2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinylether,ethoxyethyl vinylether, butoxyethyl vinyl ether, methoxyethoxyvinylether, ethoxyethoxyethyl vinylether, methoxypolyethylene glycolvinylether, tetrahydrofurfuryl vinylether, dodecyl vinylether,diethylene glycol monovinylether, 2-hydroxyethyl vinylether,2-hydroxypropyl vinylether, 4-hydroxybutyl vinylether,4-hydroxymethylcyclohexylmethyl vinylether, polyethylene glycolvinylether, chloroethyl vinylether, chlorobutyl vinylether, phenylethylvinylether, phenoxypolyethylene glycol vinylether, ethylene glycoldivinylether, butylenes glycol divinylether, hexanediol divinylether,bisphenol A alkyleneoxide divinylethers, bisphenol F alkyleneoxidedivinylethers, propyleneoxide adducts of trimethylolpropanetrivinylether, triethylene glycol divinylether, cyclohexane dimethanoldivinylether, N-vinyl-2-pyrrolidone (VP), N-vinyl caprolactam (VCap),N-vinyl imidazole (VI), n-vinyl amides, 4-vinyl pyridine, 2-vinylpyridine, styrene, 5-vinyl-2-norbomene and the like.

The non-limiting examples of monofunctional epoxy compounds includephenyl glycidylether, p-tert-butylphenyl glycidylether, butylglycidylether, 2-ethylhexyl glycidylether, allyl glycidylether,1,2-butyleneoxide, 1,3-butadienemonooxide, 1,2-epoxydodecane,epichlorohydrin, 1,2-epoxydecane, styreneoxide, cyclohexeneoxide,3-methacryloyloxymethylcylcohexeneoxide,3-acryloyloxymethylcylcohexeneoxide, 3-vinylcylcohexeneoxide, and thelike.

The non-limiting examples of multifunctional epoxy compounds include3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,3-ethyl-3-((ethyloxetane-3-yl)methoxy) methyl)oxetane, bisphenol Adiglycidylether, bisphenol F diglycidylether, bisphenol Sdiglycidylether, brominated bisphenol A diglycidylether, brominatedbisphenol F diglycidylethers, brominated bisphenol S diglycidylether,epoxy novolak resins, hydrogenated bisphenol A diglycidylethers,hydrogenated bisphenol F diglycidylethers, hydrogenated bisphenol Sdiglycidylethers,3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate,2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane,bis(3,4-epoxycyclohexylmethyl) adipate, vinylcylcohexeneoxide,4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, methylene-bis(3,4-epoxycyclohexane), dicyclopentadienediepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxyhexahydrodioctyl phthalate,epoxyhexahydrodi-2-ethylhexyl phthalate, 1,4-butanediol diglycidylether,1,6-hexanediol diglycidylether, glycerol triglycidylether,trimethylolpropane triglycidylether, polyethylene glycoldiglycidylether, polypropylene glycol diglycidylether,1,1,3-tetradecadienedioxide, limonenedioxide, 1,2,7,8-diepoxyoctane,1,2,5,6-diepoxycyclooctane, and the like.

The invention relates to curing or cross-linking or polymerizing apolymerizable material is carried out by any appropriate method known orexplored in the prior-arts by a person skilled in the art. Insight tocuring and cross-linking technology is further disclosed in“Thermosetting Polymers,” J. P. Pascault et. al. (Marcel Dekker, NewYork, 2002) and is referred and disclosed herein in its entirety.Particularly, the polymerization of reactive solution comprisingpolymerizable polymer is carried out by employing any one of the methoddisclosed in “Principles of Polymerization 4^(th) edition,” by GeorgeOdian (J. Wiley and Sons, Hoboken, N.J., 2004) and is referred anddisclosed herein in its entirety. The preferable techniques or methodsemployed by The invention to polymerize the polymers would includeUV-radiation, UV-LED, laser beam, electron beam, gamma irradiation,free-radical, cationic, anionic, thermal, exposure to e-beam and/or byemploying a high-energy source in presence of suitable photo initiatorfor the initiation of polymerization. Suitable source of radiationincluding but not limited to mercury, xenon, halogen, carbon arc lamps,sunlight, and radioactive sources.

The invention relates to material suitable for decorating(functionalizing or surface modification) the surface of a pigment. Apigment is defined as an insoluble substance, in solvent or water thatis a particle. Often it is desirable to decorate the pigment surface inorder to impart new and useful properties. For example, K. Holmberg et.al. describes technology related to surface modifications of aluminium(inorganic) pigments in Adv. Colloidal and Interface Sci. 128-130 (2006)121-134, and is referred and disclosed herein in its entirety.Additionally, organic pigments, such as polyvinyl polypyrrolidone(PVPP), are not easily functionalized. Incorporation of acetoacetatefunctionality provides for many decoration approaches to functionalizingthe surface of such particles, with either new organic and/or inorganicfeatures.

In order to induce polymerization via irradiation, often an appropriatephotoinitiator(s), which has high storage stability after being added,are incorporated to initiate the polymerization reaction system.Preferable photoinitiators are selected from the following non-limitinggroup or class of compounds such as2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenylketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morphorinopropane-1-on;benzoins e.g. benzyl dimethyl ketal; benzophenones such as benzophenone,4-phenylbenzophenone, and hydroxybenzophenone; thioxanthones such asisopropylthioxanthone and 2,4-diethylthioxanthone; acylphosphine oxides;and other special initiators such as methyl phenyl glyoxylate;bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)phenyl sulfide], a mixtureof bis[4-diphenylsulfonio]phenyl)sulfide bis(hexafluoroantimonate anddiphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate,bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)phenyl sulfide],5-2,4-cyclopentadiene-1-yl-[(1,2,3,4,5,6-.eta.)-(1-methylethyl-)benzene]-iron(1+)-hexafluorophosphate(1−)), 4-(2-hydroxytetradecanyloxy)diphenyliodonium hexafluoroantimonate, (4-hydroxynaphthyl)dimethylsulfonium hexafluoroantimonate), photo latent bases such asphoto latent diazabicyclo nonene, triphenylsulfoniumhexafluorophosphate, triphenylsulfonium hexafluoroantimonate,4-methoxyphenyldiphenylsulfonium hexafluoroantimonate,4-methoxyphenyliodonium hexafluoroantimonate,bis(4-tert-butylphenyl)iodonium tetrafluoroborate,(bis(4-tert-butylphenyl)iodonium hexafluorophosphate),(bis(4-tert-phenyl)iodonium hexafluoroantimonate),(bis[4-(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate)),Aryldiazonium salts, diaryliodonium salts, triaylsulfonium salts,triarylselenonium salts, dialkylphenacylsulfonium salts,triarylsulfoxonium salts, triethanol amine, aryloxydiarylsulfoniumsalts, and the like for example, triphenylsulfonium hexaflurophosphate,methyidiphenylsulfonium hexafluorophosphate, dimethylphenylsulfoniumhexaflurophosphate, diphenyinapththylsulfonium hexaflurophosphate,di(methoxynapththyl)methylsulfonium hexaflurophosphate,(4-octyloxyphenyl) phenyl iodonium hexafluoro antimonate,(4-octyloxyphenyl) diphenyl sulfonium hexafluoro antimonate,(4-decyloxyphenyl) phenyl iodonium hexafluoro antimonate,(4-dodecyloxyphenyl)diphenyl sulfonium hexafluoroantimonate.Particularly, employed photoinitiators include10-biphenyl-4-yl-2-isopropyl-9H-thioxanthen-10-ium hexaflurophosphate,4,4′-dimethyl iodonium hexaflurophosphate, mixed triarylsulfoniumhexaflurophosphate salts and reaction products of polyol and10-(2-carboxymethoxy)-biphenyl-4yl-2-isopropyl-9-oxo-9H-thioxanthen-10-iumhexaflurophosphate. Further, these photoinitiators are used alone or incombination thereof. Alternatively, if essential, the photoinitiator maybe used by mixing it with one or more photopolymerization accelerator,such as a benzoic acid (e.g., 4-dimethylaminobenzoic acid) or a tertiaryamine (e.g., diazabicyclo nonene (DBN)), in any appropriate ratio. Thephotoinitiator is preferably added to the photopolymerizable compositionin the range of about 0.1% to about 20% by weight.

In order to induce the Michael Addition, often an appropriate base isrequired. Preferable bases include diazabicyclo nonene (DBN),diazabicyclo undecene (DBU), tetramethylguanidine (TMG), sodiumhydroxide (NaOH), potassium hydroxide (KOH) and the like. Additionalinsight to suitable bases can be found in “Super Bases for OrganicSynthesis” edited by T Ishikawa (J. Wiley and Sons, West Sussex, U K,2009.

In one aspect, the polymerizable material may be reacted throughfree-radical polymerization in the presence of a free-radical initiator.A free-radical initiator refers to a chemical moiety, which, uponexposure to an appropriate energy source (e.g. light or heat) decomposesin to two independent uncharged fragments left with highly reactive oneunpaired electron. The contemplated free radical initiator forpolymerization would include but are not limited to various derivativesof peroxides, peresters and/or azo compounds. More particularly,selected from the group consisting of dicumyl peroxide, dibenzoylperoxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butylperoxide, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, bis(tert-butylperoxyisopropyl)benzene, and tert-butyl hydroperoxide), diacylperoxides, cumene hydroperoxide, dialkyl peroxides, hydroperoxides,ketone peroxides, monoperoxycarbonates, peroxydicarbonates,peroxyesters, and peroxyketals, including tertiary butyl perbenzoate,tertiary butyl peroctoate in diallyl phthalate, diacetyl peroxide indimethyl phthalate, dibenzoyl peroxide, 1-hydroxy cyclohexyl-1-phenylketone, bis(2,4,6-trimethyl benzoyl)phenyl phosphine, benzoin ethylether, 2,2-dimethoxy-2-phenyl acetophenone, di(p-chlorobenzoyl) peroxidein dibutyl phthalate, di(2,4-dichlorobenzoyl) peroxide with dibutylphthalate, dilauroyl peroxide, methyl ethyl ketone peroxide,cyclohexanone peroxide in dibutyl phthalate,3,5-dihydroxy-3,4-dimethyl-1,2-dioxacyclopentane, t-butylperoxy(2-ethylhexanoate), caprylyl peroxide, 2,5-dimethyl-2,5-di(benzoyl peroxy)hexane, 1-hydroxy cyclohexyl hydroperoxide-1, t-butyl peroxy (2-ethylbutyrate), 2,5-dimethyl-2,5-bis(t-butyl peroxy) hexane, cumylhydroperoxide, diacetyl peroxide, t-butyl hydroperoxide, ditertiarybutyl peroxide, 3,5-dihydroxy-3,5-dimethyl-1,2-oxacyclopentane, and1,1-bis(t-butyl peroxy)-3,3,5-trimethyl cyclohexane and di-(4-t-butylcyclohexyl) peroxydicarbonate, azo compounds such asazobisisobutyronitrile and azobiscyclohexanenitrile (e.g.,2,2′-azobis(2-methyl-propanenitrile),2,2′-azobis(2-methylbutanenitrile), and1,1′-azobis(cyclohexanecarbonitrile)) and the like mixtures andcombinations thereof. Alternatively, all of the above revealed freeradical initiator can be used for thermal based polymerization alone orappropriate mixture thereof and wherein, the polymerization reaction isinitiated through heat energy. Particular thermal initiator employed forthe polymerization of polymer would comprise 2,2′-azobis(2,4-dimethylpentanenitrile), 2,2′-azobis (2-methylpropanenitrile),2,2′-azobis (2-methylbutanenitrile), peroxides such as benzoyl peroxide,and the like. Preferably, the thermal initiator is2,2′-azobis(isobutyronitrile).

The structure of polymerizable polymer present in the reactive solutionis confirmed from appropriate spectral techniques that are known in theart and preferably employed spectral techniques would include ¹H-NMR,¹³C-NMR, and FT-IR spectra.

In one aspect, a colorant may be added. The colorant can be in the formof a pigments or dye. Combinations of pigments and dyes are alsoenvisioned. Suitable pigment materials are described in Hunger's“Industrial Organic Pigments,” Itoh's “Dictionary of Pigments,” andLeach and Pierce's “Printing Ink Manual.”

In one aspect of the invention, a solvent may be added. Suitablesolvents are described in the “Industrial Solvents Handbook, 4^(th)Edition” edited by E. W. Flick (Noyes Data Corporation, Park Ridge,N.J., 1991), which disclosure is incorporated by reference herein. Foradditional consideration of solvents, useful information is described in“Polymer Handbook, 4^(th) Edition,” edited by J. Brandrup et. al. (J.Wiley and Sons, New York, 1999), which disclosure is incorporated byreference herein.

In one process for preparing a reactive solution comprising acetoacetatepolymer is (a) producing polymerizable polymer in a low boiling solvent,(b) eliminating the low boiling solvent at atmospheric or reducedpressure; and (c) replenishing with at least one higher boiling reactivesolvent. Wherein, the solvent is selected from polar and non-polarcategory. The typical non-limiting example of the solvents employed inthe process would include toluene, xylene, cyclohexanone, chlorobenzene,methyl ethyl ketone, dichloroethane, chloroform, chloromethane,dichloromethane, carbon tetrachloride, ethylene chloride,trichloroethane, ethyl acetate, n-propyl acetate, iso-propyl acetate,2-nitropropane, any form of water (distilled, deionized or tap) andwater miscible solvents such as tetrahydrofuran, acetone, dioxane,dimethyl formamide, dimethyl sulfoxide, ethanol, methanol, propanol,isopropanol, butanol, isobutanol, ethylene glycol, ethylene glycolmonomethyl ether, and propylene glycol. The solvent is eliminated fromthe reaction mixture employing suitable techniques that are known in theart to concentrate the reaction mixture, however, the preferable methodof elimination is boiling, distilling, evaporating with or withoutvacuum.

In another aspect, application of a wide variety of compositionscomprising the modified polymers are provided, including adhesives,aerosols, agricultural compositions, anti-soil redeposition agents,batteries, beverages, biocides, block copolymers, branch copolymers,cementing compositions, cleaning compositions, comb copolymers, coatingcompositions, conductive materials, cosmetic compositions,cross-linkers, decorated pigment surfaces, dental compositions,detergents, dispersants, drugs, electronics, encapsulations, foods,graft copolymers, hair sprays, household-industrial-institutional(HI&I), inks and coatings (suitable for use as a moisture resistantinkjet recording medium), interlaminate adhesives, lithographicsolutions, membrane additive compositions, metal working fluids,oilfield compositions, paints, paper, personal care compositions,pharmaceuticals, pigment additives, plasters, plastics, printing,reactive biocides, refractive index modifiers, sequestrants, soilrelease compositions, static control agents, and wood-care compositions.

Compositions belonging to the personal care/cosmetic and pharmaceuticalarts find utility in altering, delivering an active, enhancing,improving, modifying the appearance, condition, color, health, style ofthe skin (including face, scalp, and lips), hair, nails, and oralcavity. Many examples and product forms of these compositions are known.These compositions can impart benefits that include, but are not limitedto, hair style flexibility, hair style durability, humidity resistancefor hair, color and/or color protection, moisturization, wrinklereduction, protection from ultraviolet radiation, water proofness, waterresistance, wear resistance, thermal protection, adhesion, activeingredient delivery, anti-cavity, and/or anti-gingivitis protection. Assuch, these compositions are sometimes categorized in the followingareas: skin care, hair care (both styling and non-styling), sun care,cosmetics (including color cosmetics), antiperspirants, deodorants, oralhygiene, and men's and women's personal hygiene/grooming. In some casesthese benefits and care areas overlap with another.

Skin care compositions include those materials used on the body, face,hands, lips, and/or scalp, and are beneficial for many reasons, such asfirming, anti-cellulite, moisturizing, nourishing, cleaning, reducing oreliminating the appearance of wrinkles or lentigo, toning, and/orpurifying. They also can be used to sanitize.

Consumers can identify many of the compositions that serve the sun carearea, for example after-fun, children's, beach, self-tan, sports (i.e.,being sweatproof, waterproof, resistant to running, or having added UVabsorbers and/or antioxidants), sensitive skin products (i.e., havinglow irritation to the eyes and/or skin, and/or being free of fragrancesand/or dyes), daily wear, leave-on hair creams, lotions, stylingproducts, and hair sprays. Typically, sun care products also compriseone or more UV actives, which are those organic and inorganic materialsthat scatter, absorb, and/or reflect radiation having a wavelength fromabout 100 nm to about 400 nm. In one aspect, the sun care productprotects against UV-A and/or UV-B radiation. UV-A radiation, from about320 nm to about 400 nm, has the longest wavelength within the UVspectrum, and consequently is the least energetic. While UV-A rays caninduce skin tanning, they are liable to induce adverse changes as well,especially in the case of sensitive skin or of skin, which iscontinually exposed to solar radiation. In particular UV-A rays cause aloss of skin elasticity and the appearance of wrinkles, leading topremature skin aging. UV-B rays have shorter wavelengths, from about 290nm to about 320 nm, and their higher energy can cause erythema and skinburns, which may be harmful. Alternatively, sun care products may omitUV actives, and may be regarded as a tanning oil or a tan promoter. Somesun care compositions may promote soothe skin after sun exposure, and/orbe formulated for application to the lips, hair, or the area around theeyes. Self-tan compositions, which are products that color skin withoutrequiring full sun exposure, also fit under the sun care umbrella. Themany different sun care product formats include may assume a consistencyranging from liquid to semiliquid forms (e.g., milks, creams), tothicker forms like gels, creams, pastes, and even solid- and wax-likeforms. Sun care products also may take the form of an aerosol, spray,mist, roll-on, or wipe.

Hair care compositions include shampoos, leave-on and rinse-outconditioners used for conditioning, moisturizing, repairing, haircolors, hair relaxers, and deep conditioners and treatments such as hotoils and waxes, 2-in-1 shampoo/conditioner combination products, 3-in-1shampoo/conditioner/styling agent. The many types of hair care productscan be delivered in an array of formats, including aerosol sprays, pumpsprays, gel sprays, mousses, gels, waxes, creams, pomades, spritzes,putties, lacquers, de-frizzing serums, perms, relaxants and colorants.

Color cosmetic compositions include facial make-up, eye makeup,mascaras, lip and nail products. Facial make-up compositions includefoundation (liquid, solid, and semi-solid)—skin tinted creams, liquid,sticks, mousses used as a base under make-up, rouge, face powder,blusher, highlighters, face bronzers, concealers, and 2-way cakeproducts.

Personal care/cosmetics also include eye make-up, mascaras, eyeliners,eye shadows, eyebrow pencils and eye pencils. Lip products includelipsticks, lip pencils, lip gloss, transparent bases and tinted lipmoisturizers as well as multi-function color sticks that can also beused for cheeks and eyes. Nail products include nail varnishes/enamels,nail varnish removers, treatments, home-manicure products such ascuticle softeners and nail strengtheners.

In addition to the skin, hair, and sun care compositions summarizedabove, the polymers related herein also find application in oral carecompositions. Non-limiting examples or oral care compositions includetoothpastes (including toothpaste gels), denture adhesives, whiteners,anesthetics, and dental floss and related products. These compositionsmay take any product format, such as pastes, gels, creams, solutions,dispersions, rinses, flosses, aerosols, powders, and lozenges.

Grooming products for men and women include shaving products andtoiletries, which may find use in preparing the skin and/or hair for dryor wet shaving. In addition, these compositions may help to moisturize,cool, and/or soothe skin. A variety of product forms are known, a few ofwhich are foams, gels, creams, sticks, oils, solutions, tonics, balms,aerosols, mists, sprays, and wipes.

The polymer can also be used in other personal care/cosmeticapplications, such as an absorbent material in appropriate applicationssuch as diapers, incontinence products, feminine products, and otherrelated products.

The polymers described herein also find application in bath and showercompositions, such as foams, gels, salts, oils, balls, liquids, powdersand pearls. Also included are bar soaps, body washes, shower gels,cleansers, gels, oils, foams, scrubs and creams. As a natural extensionof this category, these compositions also include liquid soaps and handsanitizers used for cleaning hands.

The polymer of the invention can be used in combination with one or moreadditional personal care/cosmetically acceptable additives chosen from,for example, conditioning agents, protecting agents, such as, forexample, hydrosoluble, liposoluble and water-insoluble UV filters,antiradical agents, antioxidants, vitamins and pro-vitamins, fixingagents, oxidizing agents, reducing agents, dyes, cleansing agents,anionic, cationic, nonionic and amphoteric surfactants, thickeners,perfumes, pearlizing agents, stabilizers, pH adjusters, filters,preservatives, hydroxy acids, various cationic, anionic and nonionicpolymers, cationic and nonionic polyether associative polyurethanes,vegetable oils, mineral oils, synthetic oils, polyols such as glycolsand glycerol, silicones, aliphatic alcohols, colorants, bleachingagents, highlighting agents and sequestrants.

For some embodiments, it may be preferred to add one or morepreservatives and/or antimicrobial agents, such as, but not limited to,benzoic acid, sorbic acid, dehydroacetic acid, piroctone olamine, DMDMhydantoin, IPBC, triclosan, bronopol, formaldehyde, isothiazolinones,nitrates/nitrites, parabens, phenoxyethanol, potassium sorbate, sodiumbenzoate, sulphites, and sulphur dioxide. Combinations of preservativesmay be used.

In other embodiments it may be desirable to incorporate preservativeboosters/solvents, select examples of which include caprylyl glycol,hexylene glycol, pentylene glycol, ethylhexylglycerin, caprylhydroxamicacid, and glyceryl caprylate. Humectants, which include glycerin,butylene glycol, propylene glycol, sorbitol, mannitol, and xylitol maybe added. Polysaccharides, such as gum Arabic, may be included as well.It may be desirable to include one or more other ingredients, such asthose described in U.S. patent publication 2010/0183532 and WO2010/105050, which disclosures are incorporated herein by reference.

These additives may be present in the composition according to theinvention in proportions that may range from about 0% to about 20% byweight in relation to the total weight of the composition. The preciseamount of each additive may be easily determined by an expert in thefield according to its nature and its function.

Examples of these co-ingredients and many others can be found in thefollowing references, each of which is herein incorporated in itsentirety by reference: “Inventory and common nomenclature of ingredientsemployed in cosmetic products,” Official Journal of the European Union,5.4.2006, pages L 97/1 through L 97/528; and International CosmeticIngredient Dictionary and Handbook, 13^(th) edition, ISBN: 1882621476,published by The Personal Care Products Council in January 2010.

Any known conditioning agent is useful in the personal care/cosmeticcompositions of this invention. Conditioning agents function to improvethe cosmetic properties of the hair, particularly softness, thickening,untangling, feel, and static electricity and may be in liquid,semi-solid, or solid form such as oils, waxes, or gums. Similarly, anyknown skin-altering agent is useful in the compositions of thisinvention. A few examples of conditioning agents include cationicpolymers, cationic surfactants and cationic silicones. Conditioningagents may be chosen from synthesis oils, mineral oils, vegetable oils,fluorinated or perfluorinated oils, natural or synthetic waxes,silicones, cationic polymers, proteins and hydrolyzed proteins, ceramidetype compounds, cationic surfactants, fatty amines, fatty acids andtheir derivatives, as well as mixtures of these different compounds.

The synthesis oils include polyolefins, e.g., poly-α-olefins such aspolybutenes, polyisobutenes and polydecenes. The polyolefins can behydrogenated. The mineral oils suitable for use in the compositions ofthe invention include hexadecane and oil of paraffin. Suitable animaland vegetable oils include sunflower, corn, soy, avocado, jojoba,squash, raisin seed, sesame seed, walnut oils, fish oils, glyceroltricaprocaprylate, Purcellin oil or liquid jojoba. Suitable natural orsynthetic oils include eucalyptus, lavender, vetiver, litsea cubeba,lemon, sandalwood, rosemary, chamomile, savory, nutmeg, cinnamon,hyssop, caraway, orange, geranium, cade, and bergamot. Suitable naturaland synthetic waxes include carnauba wax, candelila wax, alfa wax,paraffin wax, ozokerite wax, vegetable waxes such as olive wax, ricewax, hydrogenated jojoba wax, absolute flower waxes such as blackcurrant flower wax, animal waxes such as bees wax, modified bees wax(cerabellina), marine waxes and polyolefin waxes such as polyethylenewax.

The cationic polymers that may be used as a conditioning agent accordingto the invention are those known to improve the cosmetic properties ofhair treated by detergent compositions. The expression “cationicpolymer” as used herein, indicates any polymer containing cationicgroups and/or ionizable groups in cationic groups. The cationic polymersused generally have a molecular weight the average number of which fallsbetween about 500 and 5,000,000, for example between 1000 and 3,000,000.Cationic polymers may be chosen from among those containing unitsincluding primary, secondary, tertiary, and/or quaternary amine groupsthat may either form part of the main polymer chain or a side chain.Useful cationic polymers include known polyamine, polyaminoamide, andquaternary polyammonium types of polymers, such as:

homopolymers and copolymers derived from acrylic or methacrylic estersor amides. The copolymers can contain one or more units derived fromacrylamides, methacrylamides, diacetone acrylamides, acrylamides andmethacrylamides, acrylic or methacrylic acids or their esters,vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinylesters. Specific examples include: copolymers of acrylamide and dimethylamino ethyl methacrylate quaternized with dimethyl sulfate or with analkyl halide; copolymers of acrylamide and methacryloyl oxyethyltrimethyl ammonium chloride; the copolymer of acrylamide andmethacryloyl oxyethyl trimethyl ammonium methosulfate; copolymers ofvinyl pyrrolidone/dialkylaminoalkyl acrylate or methacrylate, optionallyquaternized, such as the products sold under the name Gafquat® byInternational Specialty Products; the dimethyl amino ethylmethacrylate/vinyl caprolactam/vinyl pyrrolidone terpolymers, such asthe product sold under the name Gaffix® VC 713 by InternationalSpecialty Products; the vinyl pyrrolidone/methacrylamidopropyldimethylamine copolymer, marketed under the name Styleze® CC-10 byInternational Specialty Products; the vinyl pyrrolidone/quaternizeddimethyl amino propyl methacrylamide copolymers such as the product soldunder the name Gafquat® HS-100 by International Specialty Products; andthe vinyl pyrrolidone/dimethylaminopropyl methacrylamide/C₉-C₂₄alkyldimethylaminopropyl methacrylic acid quaternized terpolymersdescribed in U.S. Pat. No. 6,207,778 and marketed under the nameStyleze® W-20 by International Specialty Products.

derivatives of cellulose ethers containing quaternary ammonium groups,such as hydroxy ethyl cellulose quaternary ammonium that has reactedwith an epoxide substituted by a trimethyl ammonium group.

derivatives of cationic cellulose such as cellulose copolymers orderivatives of cellulose grafted with a hydrosoluble quaternary ammoniummonomer, as described in U.S. Pat. No. 4,131,576, such as the hydroxyalkyl cellulose, and the hydroxymethyl-, hydroxyethyl- orhydroxypropyl-cellulose grafted with a salt of methacryloyl ethyltrimethyl ammonium, methacrylamidopropyl trimethyl ammonium, or dimethyldiallyl ammonium.

cationic polysaccharides such as described in U.S. Pat. Nos. 3,589,578and 4,031,307, guar gums containing cationic trialkyl ammonium groupsand guar gums modified by a salt, e.g., chloride of 2,3-epoxy propyltrimethyl ammonium.

polymers composed of piperazinyl units and alkylene or hydroxy alkylenedivalent radicals with straight or branched chains, possibly interruptedby atoms of oxygen, sulfur, nitrogen, or by aromatic or heterocycliccycles, as well as the products of the oxidation and/or quaternizationof such polymers.

water-soluble polyamino amides prepared by polycondensation of an acidcompound with a polyamine. These polyamino amides may be reticulated.

derivatives of polyamino amides resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids followed by alkylationby bi-functional agents.

polymers obtained by reaction of a polyalkylene polyamine containing twoprimary amine groups and at least one secondary amine group with adioxycarboxylic acid chosen from among diglycolic acid and saturateddicarboxylic aliphatic acids having 3 to 8 atoms of carbon. Suchpolymers are described in U.S. Pat. Nos. 3,227,615 and 2,961,347.

the cyclopolymers of alkyl dialyl amine or dialkyl diallyl ammonium suchas the homopolymer of dimethyl diallyl ammonium chloride and copolymersof diallyl dimethyl ammonium chloride and acrylamide.

quaternary diammonium polymers such as hexadimethrine chloride. Polymersof this type are described particularly in U.S. Pat. Nos. 2,273,780,2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378,3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617,4,025,627, 4,025,653, 4,026,945, and 4,027,020.

quaternary polyammonium polymers, including, for example, Mirapol® A 15,Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175 products sold by Miranol.

the quaternary polymers of vinyl pyrrolidone and vinyl imidazole such asthe products sold under the names Luviquat® FC 905, FC 550, and FC 370by BASF.

quaternary polyamines.

reticulated polymers known in the art.

Other cationic polymers that may be used within the context of theinvention are cationic proteins or hydrolyzed cationic proteins,polyalkyleneimines such as polyethyleneimines, polymers containing vinylpyridine or vinyl pyridinium units, condensates of polyamines andepichlorhydrins, quaternary polyurethanes, and derivatives of chitin. Inone aspect, the cationic polymers may be derivatives of quaternarycellulose ethers, the homopolymers and copolymers of dimethyl diallylammonium chloride, quaternary polymers of vinyl pyrrolidone and vinylimidazole, and mixtures thereof.

The conditioning agent can be any silicone known by those skilled in theart to be useful as a conditioning agent. The silicones suitable for useaccording to the invention include polyorganosiloxanes that areinsoluble in the composition. The silicones may be present in the formof oils, waxes, polymers, or gums. They may be volatile or non-volatile.The silicones can be selected from polyalkyl siloxanes, polyarylsiloxanes, polyalkyl aryl siloxanes, silicone gums and polymers, andpolyorgano siloxanes modified by organofunctional groups, and mixturesthereof. Suitable polyalkyl siloxanes include polydimethyl siloxaneswith terminal trimethyl silyl groups or terminal dimethyl silanol groups(dimethiconol) and polyalkyl (C₁-C₂₀) siloxanes. Suitable polyalkyl arylsiloxanes include polydimethyl methyl phenyl siloxanes and polydimethyldiphenyl siloxanes, linear or branched. The silicone gums suitable foruse herein include polydiorganosiloxanes including those having anumber-average molecular weight between 200,000 and 1,000,000, usedalone or mixed with a solvent. Examples include polymethyl siloxane,polydimethyl siloxane/methyl vinyl siloxane gums, polydimethylsiloxane/diphenyl siloxane, polydimethyl siloxane/phenyl methyl siloxaneand polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxane.Suitable silicone polymers include silicones with a dimethyl/trimethylsiloxane structure and polymers of the trimethyl siloxysilicate type.The organo-modified silicones suitable for use in the invention includesilicones such as those previously defined and containing one or moreorganofunctional groups attached by means of a hydrocarbon radical andgrafted siliconated polymers. In one embodiment the silicones are aminofunctional silicones. The silicones may be used in the form ofemulsions, nano-emulsions, or micro-emulsions.

The conditioning agent can be a protein or hydrolyzed cationic ornon-cationic protein. Examples of these compounds include hydrolyzedcollagens having triethyl ammonium groups, hydrolyzed collagens havingtrimethyl ammonium and trimethyl stearyl ammonium chloride groups,hydrolyzed animal proteins having trimethyl benzyl ammonium groups(benzyltrimonium hydrolyzed animal protein), hydrolyzed proteins havinggroups of quaternary ammonium on the polypeptide chain, including atleast one C₁-C₁₈ alkyl. Hydrolyzed proteins include Croquat™ L, in whichthe quaternary ammonium groups include a C₁₂ alkyl group, Croquat™ M, inwhich the quaternary ammonium groups include C₁₀-C₁₈ alkyl groups,Croquat™ S in which the quaternary ammonium groups include a C₁₈ alkylgroup and Crotein Q in which the quaternary ammonium groups include atleast one C₁-C₁₈ alkyl group. These products are sold by Croda. Theconditioning agent can comprise quaternized vegetable proteins such aswheat, corn, or soy proteins such as cocodimonium hydrolyzed wheatprotein, laurdimonium hydrolyzed wheat protein and steardimoniumhydrolyzed wheat protein.

The conditioning agent can be a ceramide type of compound such as aceramide, a glycoceramide, a pseudoceramide, or a neoceramide. Thesecompounds can be natural or synthetic. Compounds of the ceramide typeare, for example, described in Patents pending DE4424530, DE4424533,DE4402929, DE4420736, WO95/23807, WO94/07844, EP-A-0646572, WO95/16665,FR-2 673 179, EP-A-0227994, WO 94/07844, WO 94/24097, and WO 94/10131.Ceramide type compounds useful herein include 2-N-linoleoylamino-octadecane-1,3-diol, 2-N-oleoyl amino-octadecane-1, 3-diol,2-N-palmitoyl amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3-diol, 2-N-behenoyl amino-octadecane-1,3-diol,2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3,4-triol, N-stearoyl phytosphingosine, 2-N-palmitoylamino-hexadecane-1,3-diol, bis-(N-hydroxy ethyl N-cetyl) malonamide,N(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxy propyl) amide of cetylic acid,N-docosanoyl N-methyl-D-glucamine and mixtures of such compounds.

The conditioning agent can be a cationic surfactant such as a salt of aprimary, secondary, or tertiary fatty amine, optionallypolyoxyalkylenated, a quaternary ammonium salt, a derivative ofimidazoline, or an amine oxide. Suitable examples include mono-, di-, ortri-alkyl quaternary ammonium compounds with a counter-ion such as achloride, methosulfate, tosylate, etc. including, but not limited to,cetrimonium chloride, dicetyldimonium chloride, behentrimoniummethosulfate, and the like. The presence of a quaternary ammoniumcompound in conjunction with the polymer described above reduces staticand enhances combing of hair in the dry state. The polymer also enhancesthe deposition of the quaternary ammonium compound onto the hairsubstrate thus enhancing the conditioning effect of hair.

The conditioning agent can be any fatty amine known to be useful as aconditioning agent; e.g. dodecyl, cetyl or stearyl amines, such asstearamidopropyl dimethylamine. The conditioning agent can be a fattyacid or derivatives thereof known to be useful as conditioning agents.Suitable fatty acids include myristic acid, palmitic acid, stearic acid,behenic acid, oleic acid, linoleic acid, and isostearic acid. Thederivatives of fatty acids include carboxylic ester acids includingmono-, di-, tri- and tetra-carboxylic acids.

The conditioning agent can be a fluorinated or perfluorinated oil.Fluorinated oils include perfluoropolyethers described in EP-A-486135and the fluorohydrocarbon compounds described in WO 93/11103. Thefluoridated oils may also be fluorocarbons such as fluoramines, e.g.,perfluorotributylamine, fluoridated hydrocarbons, such asperfluorodecahydronaphthalene, fluoroesters, and fluoroethers. Ofcourse, mixtures of two or more conditioning agents can be used.

The conditioning agent or agents can be present in an amount from about0.001% to about 20%, particularly from about 0.01% to about 10%, andeven more particularly from about 0.1% to about 3% by weight based onthe total weight of the final composition. The personal care/cosmeticcompositions of the invention can contain one or more protecting agentsin combination with the above-described polymer to prevent or limit thedegrading effects of natural physical and/or chemical assaults on thekeratinous materials.

The protecting agent can be chosen from hydrosoluble, liposoluble andwater-insoluble UV filters, antiradical agents, antioxidants, vitaminsand pro-vitamins. The above-described cationic polymer enhances thedeposition of these materials onto the hair or skin substrate enhancingprotection of hair to UV damage. Organic UV filters (systems that filterout UV rays) can be chosen from among hydrosoluble or liposolublefilters, whether siliconated or nonsiliconated, and mineral oxideparticles, the surface of which may be treated. Hydrosoluble organic UVfilters may be chosen from para-amino benzoic acid and its salts,anthranilic acid and its salts, salicylic acid and its salts, hydroxycinnamic acid and its salts, sulfonic derivatives of benzothiazoles,benzimidizoles, benzoxazoles and their salts, sulfonic derivatives ofbenzophenone and their salts, sulfonic derivatives of benzylidenecamphor and their salts, derivatives of benzylidene camphor substitutedby a quaternary amine and their salts, derivatives ofphthalydene-camphosulfonic acids and their salts, sulfonic derivativesof benzotriazole, and mixtures thereof. Hydrophilic polymers, which havelight-protective qualities against UV rays, can be used. These includepolymers containing benzylidene camphor and/or benzotriazole groups.

Suitable liposoluble organic UV filters include derivatives ofpara-aminobenzoic acid, such as the esters or amides ofpara-aminobenzoic acid; derivatives of salicylic acid; derivatives ofbenzophenone; derivatives of dibenzoyl methane; derivatives of diphenylacrylates; derivatives of benzofurans; UV filter polymers containing oneor more silico-organic residues; esters of cinnamic acid; derivatives ofcamphor; derivatives of trianilino-s-triazine; the ethylic esterurocanic acid; benzotriazoles; derivatives of hydroxy phenyl triazine;bis-resorcinol-dialkyl amino triazine; and mixtures thereof. Theliposoluble (or lipophilic) organic UV filter can be chosen from octylsalicylate; 4-tert-butyl-4′-methoxy dibenzoyl methane; octocrylene;4-methoxy cinnamate; 2-ethylhexyl [2-ethylhexyl 4-methoxycinnamate]; and2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy] disiloxanyl]propynyl] phenol. Other UV filters that may beuseful are derivatives of benzophenones such as 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxy benzophenone,derivatives of benzalmalonates such as poly dimethyl/methyl(3(4-(2,2-bis-ethoxy carbonyl vinyl)-phenoxy)-propenyl) siloxane,derivatives of benzylidene camphor such as b-b′ camphosulfonic [1-4divinylbenzene] acid and derivatives of benzimidazole such as2-phenyl-benzimidazol-5-sulfonic acid. Water-insoluble UV filtersinclude various mineral oxides. The mineral oxides may be selected fromamong titanium oxides, zinc oxides, and cerium oxides. The mineraloxides can be used in the form of ultrafine nanoparticles. For example,the UV filters can include Escalol® HP-610 (dimethylpabamido propyllaurdimonium tosylate and propylene glycol stearate) or Crodasorb HP(polyquarternium 59).

The antioxidants or antiradical agents can be selected from phenols suchas BHA (tert-butyl-4-hydroxy anisole), BHT (2,6-di-tert-butyl-p-cresol),TBHQ (tert-butyl hydroquinone), polyphenols such as proanthocyanodicoligomers, flavonoids, hindered amines such as tetra amino piperidine,erythorbic acid, polyamines such as spermine, cysteine, glutathione,superoxide dismutase, and lactoferrin.

The vitamins can be selected from ascorbic acid (vitamin C), vitamin E,vitamin E acetate, vitamin E phosphate, B vitamins such as B3 and B5,vitamin PP, vitamin A, and derivatives thereof. The provitamins can beselected from panthenol and retinol.

The protecting agent can be present in an amount from about 0.001% toabout 20% by weight, particularly from about 0.01% to about 10% byweight, and more particularly from 0.1% to about 5% by weight of thetotal weight of the final composition.

The composition of the invention can contain a fixing agent incombination with the above-described polymer. The fixing agent can be ananionic polymer chosen from polymers containing carboxylic units derivedfrom unsaturated carboxylic mono- or polyacids of the formula:

in which n is a whole number from 0 to 10, A₁ denotes a methylene group,optionally bonded to the carbon atom of the unsaturated group or to aneighboring methylene group when n is greater than 1 by means of aheteroatom like oxygen or sulfur, R₇ denotes a hydrogen atom, a phenylor benzyl group, R₈ denotes a hydrogen atom, a lower alkyl or carboxylgroup, R₉ denotes a hydrogen atom, a lower alkyl group, a —CH₂—COOH,phenyl or benzyl group and polymers containing units derived fromsulfonic acid like vinylsulfonic, styrenesulfonic,acrylamidoalkylsulfonic units.

The fixing agent can be an amphoteric polymer chosen from the polymercontaining recurring units derived from:

at least one monomer chosen from acrylamides or methacrylamidessubstituted on the nitrogen with an alkyl radical,

at least one acid copolymer containing one or more reactive carboxylgroups, and

at least one basic comonomer, such as esters with primary, secondary,tertiary, and quaternary amino substituents of acrylic and methacrylicacids and the product of quaternization of dimethylaminoethylmethacrylate with dimethyl or diethyl sulfate.

The fixing agent can be a nonionic polymer chosen frompolyalkyloxazolines; vinyl acetate homopolymers; vinyl acetate andacrylic ester copolymers; vinyl acetate and ethylene copolymers; vinylacetate and maleic ester copolymers; polyethylene and maleic anhydridecopolymers; homopolymers of alkyl acrylates; homopolymers of alkylmethacrylates; copolymers of acrylic esters; copolymers of alkylacrylates and alkyl methacrylates; copolymers of acrylonitrile and anonionic monomer chosen from among butadiene and alkyl (meth)acrylates;copolymers of alkyl acrylate and urethane; and polyamides. The fixingagent can be a functionalized or unfunctionalized, silicone ornonsilicone polyurethane. The fixing polymer can be a polymer of thegrafted silicone type containing a polysiloxane portion and a portionconsisting of a nonsilicone organic chain, with one of the two portionsforming the main chain of the polymer, and with the other being graftedonto the main chain.

The fixing agent can be present in the composition in a relative weightconcentration between about 0.1% to about 10%, for example, from about0.5% to about 5%.

The personal care/cosmetic composition of the invention can contain anoxidizing agent in combination with the above-described polymer. Theoxidizing agent can be chosen from the group of hydrogen peroxide, ureaperoxide, alkali metal bromates, ferricyanides, persalts, and redoxenzymes, optionally with their respective donor or cofactor. Forexample, the oxidizing agent can be hydrogen peroxide. The oxidizingagent can be a solution of oxygenated water whose titer varies from 1 to40 volumes.

The personal care/cosmetic composition of the invention can contain atleast one reducing agent in combination with the above-described polymerin amounts from about 0.01% to about 30%, particularly from about 0.05%to about 20% of the total weight of the composition. The reducing agentscan be selected from thiols, like cysteine, thioglycolic acid,thiolactic acid, their salts and esters, cysteamine, and its salts orsulfites. In the case of compositions intended for bleaching, ascorbicacid, its salts and its esters, erythorbic acid, its salts and itsesters, and sulfinates, like sodium hydroxymethanesulfinate can be used.

The personal care/cosmetic composition of the invention can contain adye in combination with the above-described polymer. The dye can beselected from the group consisting of neutral acid or cationicnitrobenzene dyes, neutral acid or cationic azo dyes, quinone dyes,neutral, acid or cationic anthraquinone dyes, azine dyes, triarylmethanedyes, indoamine dyes and natural dyes. The dye or dyes can be present ina concentration from about 0.001% to about 20%, and particularly fromabout 0.005% to about 10% based on the total weight of the composition.

The personal care/cosmetic composition of the invention can contain atleast one amphoteric polymer or a cationic polymer in combination withthe above-described polymer. Suitable cationic polymers include apoly(quaternary ammonium) consisting of recurrent units corresponding tothe following formulae (W) and (U):

Suitable amphoteric polymers include a copolymer containing at least oneacrylic acid and a dimethyldiallyammonium salt as a monomer. Thecationic or amphoteric polymer or polymers can be present in an amountfrom about 0.01% to about 10%, particularly from about 0.05% to about5%, and more particularly from about 0.1% to about 3% by weight of thetotal weight of the composition.

In addition, the personal care/cosmetic compositions can include atleast one surfactant in combination with the above-described polymer.The surfactant can be present in an amount from about 0.1% to about 60%,particularly from about 1% to about 40%, and more particularly fromabout 5% to about 30% by weight based on the total weight of thecomposition. The surfactant may be chosen from among anionic,amphoteric, or non-ionic surfactants, or mixtures of them known to beuseful in personal care/cosmetic compositions.

One or more suitable thickeners or viscosity increasing agents may beincluded in combination with the above-described polymer in the personalcare/cosmetic compositions of the invention. Suitable thickeners and/orviscosity increasing agents include: Acetamide MEA;Acrylamide/Ethalkonium Chloride Acrylate Copolymer;Acrylamide/Ethyltrimonium Chloride Acrylate/Ethalkonium ChlorideAcrylate Copolymer; Acrylamides Copolymer; Acrylamide/Sodium AcrylateCopolymer; Acrylamide/Sodium Acryloyldimethyltaurate Copolymer;Acrylates/Acetoacetoxyethyl Methacrylate Copolymer;Acrylates/Beheneth-25 Methacrylate Copolymer; Acrylates/C10-30 AlkylAcrylate Crosspolymer; Acrylates/Ceteth-20 Itaconate Copolymer;Acrylates/Ceteth-20 Methacrylate Copolymer; Acrylates/Laureth-25Methacrylate Copolymer; Acrylates/Palmeth-25 Acrylate Copolymer;Acrylates/Palmeth-25 Itaconate Copolymer; Acrylates/Steareth-50 AcrylateCopolymer; Acrylates/Steareth-20 Itaconate Copolymer;Acrylates/Steareth-20 Methacrylate Copolymer; Acrylates/StearylMethacrylate Copolymer; Acrylates/Vinyl Isodecanoate Crosspolymer;Acrylic Acid/Acrylonitrogens Copolymer; Adipic Acid/Methyl DEACrosspolymer; Agar; Agarose; Alcaligenes Polysaccharides; Algin; AlginicAcid; Almondamide DEA; Almondamidopropyl Betaine; Aluminum/MagnesiumHydroxide Stearate; Ammonium Acrylates/Acrylonitrogens Copolymer;Ammonium Acrylates Copolymer; Ammonium Acryloyldimethyltaurate/VinylFormamide Copolymer; Ammonium Acryloyldimethyltaurate/VP Copolymer;Ammonium Alginate, Ammonium Chloride; Ammonium PolyacryloyldimethylTaurate; Ammonium Sulfate; Amylopectin; Apricotamide DEA;Apricotamidopropyl Betaine; Arachidyl Alcohol; Arachidyl Glycol; ArachisHypogaea (Peanut) Flour; Ascorbyl Methylsilanol Pectinate; AstragalusGummifer Gum; Attapulgite; Avena Sativa (Oat) Kernel Flour; AvocadamideDEA; Avocadamidopropyl Betaine, Azelamide MEA; Babassuamide DEA;Babassuamide MEA; Babassuamidopropyl Betaine; Behenamide DEA; BehenamideMEA, Behenamidopropyl Betaine; Behenyl Betaine; Bentonite; ButoxyChitosan, Caesalpinia Spinosa Gum; Calcium Alginate; CalciumCarboxymethyl Cellulose; Calcium Carrageenan; Calcium Chloride; CalciumPotassium Carbomer; Calcium Starch Octenylsuccinate; C20-40 AlkylStearate; Canolamidopropyl Betaine; Capramide DEA;Capryl/Capramidopropyl Betaine; Carbomer; Carboxybutyl Chitosan;Carboxymethyl Cellulose Acetate Butyrate; Carboxymethyl Chitin;Carboxymethyl Chitosan; Carboxymethyl Dextran; CarboxymethylHydroxyethylcellulose; Carboxymethyl Hydroxypropyl Guar; Carnitine;Cellulose Acetate Propionate Carboxylate; Cellulose Gum; CeratoniaSiliqua Gum; Cetearyl Alcohol; Cetyl Alcohol; Cetyl Babassuate; CetylBetaine; Cetyl Glycol; Cetyl Hydroxyethylcellulose; Chimyl Alcohol;Cholesterol/HDI/Pullulan Copolymer; Cholesteryl Hexyl DicarbamatePullulan; Citrus Aurantium Dulcis (Orange) Peel Extract; Cocamide DEA;Cocamide MEA; Cocamide MIPA; Cocamidoethyl Betaine; CocamidopropylBetaine; Cocamidopropyl Hydroxysultaine; Coco-Betaine;Coco-Hydroxysultaine; Coconut Alcohol; Coco/Oleamidopropyl Betaine;Coco-Sultaine; Cocoyl Sarcosinamide DEA; Cornamide/Cocamide DEA;Cornamide DEA; Croscarmellose; Crosslinked Bacillus/Glucose/SodiumGlutamate Ferment; Cyamopsis Tetragonoloba (Guar) Gum; Decyl Alcohol;Decyl Betaine; Dehydroxanthan Gum; Dextrin; Dibenzylidene Sorbitol;Diethanolaminooleamide DEA; Diglycol/CHDM/Isophthalates/SIP Copolymer;Dihydroabietyl Behenate; Dihydrogenated Tallow Benzylmonium Hectorite;Dihydroxyaluminum Aminoacetate; Dimethicone/PEG-10 Crosspolymer;Dimethicone/PEG-15 Crosspolymer; Dimethicone Propyl PG-Betaine;Dimethylacrylamide/Acrylic Acid/Polystyrene Ethyl MethacrylateCopolymer; Dimethylacrylamide/Sodium AcryloyldimethyltaurateCrosspolymer; Disteareth-100 IPDI; DMAPA Acrylates/AcrylicAcid/Acrylonitrogens Copolymer; Erucamidopropyl Hydroxysultaine;Ethylene/Sodium Acrylate Copolymer; Gelatin; Gellan Gum; GlycerylAlginate; Glycine Soja (Soybean) Flour; Guar HydroxypropyltrimoniumChloride; Hectorite; Hyaluronic Acid; Hydrated Silica; HydrogenatedPotato Starch; Hydrogenated Tallow; Hydrogenated Tallowamide DEA;Hydrogenated Tallow Betaine; Hydroxybutyl Methylcellulose; HydroxyethylAcrylate/Sodium Acryloyldimethyl Taurate Copolymer;Hydroxyethylcellulose; Hydroxyethyl Chitosan; HydroxyethylEthylcellulose; Hydroxyethyl Stearamide-MIPA;Hydroxylauryl/Hydroxymyristyl Betaine; Hydroxypropylcellulose;Hydroxypropyl Chitosan; Hydroxypropyl Ethylenediamine Carbomer;Hydroxypropyl Guar; Hydroxypropyl Methylcellulose; HydroxypropylMethylcellulose Stearoxy Ether; Hydroxypropyl Starch; HydroxypropylStarch Phosphate; Hydroxypropyl Xanthan Gum; Hydroxystearamide MEA;Isobutylene/Sodium Maleate Copolymer; Isostearamide DEA; IsostearamideMEA; Isostearamide MIPA; Isostearamidopropyl Betaine; Lactamide MEA;Lanolinamide DEA; Lauramide DEA; Lauramide MEA; Lauramide MIPA;Lauramide/Myristamide DEA; Lauramidopropyl Betaine; LauramidopropylHydroxysultaine; Laurimino Bispropanediol; Lauryl Alcohol; LaurylBetaine; Lauryl Hydroxysultaine; Lauryl/Myristyl Glycol HydroxypropylEther; Lauryl Sultaine; Lecithinamide DEA; Linoleamide DEA; LinoleamideMEA; Linoleamide MIPA; Lithium Magnesium Silicate; Lithium MagnesiumSodium Silicate; Macrocystis Pyrifera (Kelp); Magnesium Alginate;Magnesium/Aluminum/Hydroxide/Carbonate; Magnesium Aluminum Silicate;Magnesium Silicate; Magnesium Trisilicate; Methoxy PEG-22/Dodecyl GlycolCopolymer; Methylcellulose; Methyl Ethylcellulose; MethylHydroxyethylcellulose; Microcrystalline Cellulose; MilkamidopropylBetaine; Minkamide DEA; Minkamidopropyl Betaine; MIPA-Myristate;Montmorillonite; Moroccan Lava Clay; Myristamide DEA; Myristamide MEA;Myristamide MIPA; Myristamidopropyl Betaine; MyristamidopropylHydroxysultaine; Myristyl Alcohol; Myristyl Betaine; Natto Gum;Nonoxynyl Hydroxyethylcellulose; Oatamide MEA; Oatamidopropyl Betaine;Octacosanyl Glycol Isostearate; Octadecene/MA Copolymer; Oleamide DEA;Oleamide MEA; Oleamide MIPA; Oleamidopropyl Betaine; OleamidopropylHydroxysultaine; Oleyl Betaine; Olivamide DEA; Olivamidopropyl Betaine;Oliveamide MEA; Palmamide DEA; Palmamide MEA; Palmamide MIPA;Palmamidopropyl Betaine; Palmitamide DEA; Palmitamide MEA;Palmitamidopropyl Betaine; Palm Kernel Alcohol; Palm Kemelamide DEA;Palm Kemelamide MEA; Palm Kemelamide MIPA; Palm KernelamidopropylBetaine; Peanutamide MEA; Peanutamide MIPA; Pectin; PEG-800;PEG-Crosspolymer; PEG-150/Decyl Alcohol/SMDI Copolymer; PEG-175Diisostearate; PEG-190 Distearate; PEG-15 Glyceryl Tristearate; PEG-140Glyceryl Tristearate; PEG-240/HDI Copolymer Bis-Decyltetradeceth-20Ether; PEG-100/IPDI Copolymer; PEG-180/Laureth-50/TMMG Copolymer;PEG-10/Lauryl Dimethicone Crosspolymer; PEG-15/Lauryl DimethiconeCrosspolymer; PEG-2M; PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M;PEG-25M; PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M;PEG-120 Methyl Glucose Trioleate; PEG-180/Octoxynol-40/TMMG Copolymer;PEG-150 Pentaerythrityl Tetrastearate; PEG-4 Rapeseedamide;PEG-150/Stearyl Alcohol/SMDI Copolymer; Phaseolus Angularis Seed Powder;Polianthes Tuberosa Extract; Polyacrylate-3; Polyacrylic Acid;Polycyclopentadiene; Polyether-1; Polyethylene/Isopropyl Maleate/MACopolyol; Polyglyceryl-3 Disiloxane Dimethicone; Polyglyceryl-3Polydimethylsiloxyethyl Dimethicone; Polymethacrylic Acid;Polyquatemium-52; Polyvinyl Alcohol; Potassium Alginate; PotassiumAluminum Polyacrylate; Potassium Carbomer; Potassium Carrageenan;Potassium Chloride; Potassium Palmate; Potassium Polyacrylate; PotassiumSulfate; Potato Starch Modified; PPG-2 Cocamide; PPG-1 HydroxyethylCaprylamide; PPG-2 Hydroxyethyl Cocamide; PPG-2 HydroxyethylCoco/Isostearamide; PPG-3 Hydroxyethyl Soyamide; PPG-14 Laureth-60 HexylDicarbamate; PPG-14 Laureth-60 Isophoryl Dicarbamate; PPG-14 Palmeth-60Hexyl Dicarbamate; Propylene Glycol Alginate; PVP/Decene Copolymer; PVPMontmorillonite; Pyrus Cydonia Seed; Pyrus Malus (Apple) Fiber;Rhizobian Gum; Ricebranamide DEA; Ricinoleamide DEA; Ricinoleamide MEA;Ricinoleamide MIPA; Ricinoleamidopropyl Betaine; Ricinoleic Acid/AdipicAcid/AEEA Copolymer; Rosa Multiflora Flower Wax; Sclerotium Gum;Sesamide DEA; Sesamidopropyl Betaine; Sodium Acrylate/AcryloyldimethylTaurate Copolymer; Sodium Acrylates/Acrolein Copolymer; SodiumAcrylates/Acrylonitrogens Copolymer; Sodium Acrylates Copolymer; SodiumAcrylates Crosspolymer; Sodium Acrylate/Sodium AcrylamidomethylpropaneSulfonate Copolymer; Sodium Acrylates/Vinyl Isodecanoate Crosspolymer;Sodium Acrylate/Vinyl Alcohol Copolymer; Sodium Carbomer; SodiumCarboxymethyl Chitin; Sodium Carboxymethyl Dextran; Sodium CarboxymethylBeta-Glucan; Sodium Carboxymethyl Starch; Sodium Carrageenan; SodiumCellulose Sulfate; Sodium Chloride; Sodium Cyclodextrin Sulfate; SodiumHydroxypropyl Starch Phosphate; Sodium Isooctylene/MA Copolymer; SodiumMagnesium Fluorosilicate; Sodium Oleate; Sodium Palmitate; Sodium PalmKernelate; Sodium Polyacrylate; Sodium Polyacrylate Starch; SodiumPolyacryloyldimethyl Taurate; Sodium Polygamma-Glutamate; SodiumPolymethacrylate; Sodium Polystyrene Sulfonate; Sodium Silicoaluminate;Sodium Starch Octenylsuccinate; Sodium Stearate; Sodium StearoxyPG-Hydroxyethylcellulose Sulfonate; Sodium Styrene/Acrylates Copolymer;Sodium Sulfate; Sodium Tallowate; Sodium Tauride Acrylates/AcrylicAcid/Acrylonitrogens Copolymer; Sodium Tocopheryl Phosphate; SolanumTuberosum (Potato) Starch; Soyamide DEA; Soyamidopropyl Betaine;Starch/Acrylates/Acrylamide Copolymer; Starch HydroxypropyltrimoniumChloride; Stearamide AMP; Stearamide DEA; Stearamide DEA-Distearate;Stearamide DIBA-Stearate; Stearamide MEA; Stearamide MEA-Stearate;Stearamide MIPA; Stearamidopropyl Betaine; Steareth-60 Cetyl Ether;Steareth-100/PEG-136/HDI Copolymer; Stearyl Alcohol; Stearyl Betaine;Sterculia Urens Gum; Synthetic Fluorphlogopite; Tallamide DEA; TallowAlcohol; Tallowamide DEA; Tallowamide MEA; Tallowamidopropyl Betaine;Tallowamidopropyl Hydroxysultaine; Tallowamine Oxide; Tallow Betaine;Tallow Dihydroxyethyl Betaine; Tamarindus Indica Seed Gum; TapiocaStarch; TEA-Alginate; TEA-Carbomer; TEA-Hydrochloride; Trideceth-2Carboxamide MEA; Tridecyl Alcohol; Triethylene Glycol Dibenzoate;Trimethyl Pentanol Hydroxyethyl Ether; Triticum Vulgare (Wheat) GermPowder; Triticum Vulgare (Wheat) Kernel Flour; Triticum Vulgare (Wheat)Starch; Tromethamine Acrylates/Acrylonitrogens Copolymer; TromethamineMagnesium Aluminum Silicate; Undecyl Alcohol; Undecylenamide DEA;Undecylenamide MEA; Undecylenamidopropyl Betaine; Welan Gum; WheatGermamide DEA; Wheat Germamidopropyl Betaine; Xanthan Gum; YeastBeta-Glucan; Yeast Polysaccharides and Zea Mays (Corn) Starch.

In one such embodiment, the thickeners or viscosity increasing agentsinclude carbomers, Aculyn™ and Stabileze®, e.g., crosslinked acrylicacid, crosslinked poly(methylvinyl ether/maleic anhydride) copolymer,acrylamides, carboxymethyl cellulose, and the like.

The personal care/cosmetic compositions may be used to wash and treatkeratinous material such as hair, skin, eyelashes, eyebrows,fingernails, lips, and hairy skin.

The personal care/cosmetic compositions can be detergent compositionssuch as shampoos, bath gels, and bubble baths. In this mode, thecompositions will comprise a generally aqueous washing base. Thesurfactant or surfactants that form the washing base may be chosen aloneor in blends, from known anionic, amphoteric, or non-ionic surfactants.The quantity and quality of the washing base must be sufficient toimpart a satisfactory foaming and/or detergent value to the finalcomposition. The washing base can be from about 4% to about 50% byweight, particularly from about 6% to about 35% by weight, and even moreparticularly from about 8% to about 25% by weight of the total weight ofthe final composition.

The pH of the composition applied to the keratinous material isgenerally between 2 and 12. In one embodiment, the pH is from about 3 toabout 8, and may be adjusted to the desired value by means of acidifyingor alkalinizing agents that are well known in the state of the art.Thus, the composition of the invention can contain at least onealkalizing or acidifying agent in amounts from about 0.01% to about 30%based on the total weight of the composition.

The alkalizing agent can be chosen from ammonia, alkali carbonates,alkanolamines, like mono-, di- and triethanolamines, as well as theirderivatives, hydroxyalkylamines and ethoxylated and/or propoxylatedethylenediamines, sodium or potassium hydroxides and compounds of thefollowing formula:

in which R is a propylene residue optionally substituted with anhydroxyl group or a C₁-C₄ alkyl radical; R₃₈, R₃₉, R₄₀ and R₄₁,identical or different, represent a hydrogen atom, a C₁-C₄ alkyl radicalor C₁-C₄ hydroxyalkyl radical.

The acidifying agent can be chosen from mineral or organic acids, likehydrochloric acid, orthophosphoric acid, carboxylic acids like tartaricacid, citric acid, or lactic acid, or sulfonic acids, and the like.

The personal care/cosmetic compositions of the invention may include aphysiological and cosmetically acceptable medium. Such medium mayconsist exclusively of water, a cosmetically acceptable solvent, or ablend of water and a cosmetically acceptable solvent, such as a loweralcohol composed of C₁ to C₄, such as ethanol, isopropanol, t-butanol,n-butanol, alkylene glycols such as propylene glycol, and glycol ethers.Alternatively, the personal care/cosmetic compositions can be anhydrous.

Generally, personal care/cosmetic compositions can be prepared by simplemixing procedures well known in the art. The invention provides a methodfor treating keratinous material including the skin or hair, by applyingto skin or keratinous materials a personal care/cosmetic composition asdescribed above, and then eventually rinsing it with water. Accordingly,the method makes it possible to maintain the hairstyle, treatment, care,washing, or make-up removal of the skin, the hair, and any otherkeratinous material. The personal care/cosmetic compositions may alsotake the form of after-shampoo compositions, to be rinsed off or not,for permanents, straightening, waving, dyeing, or bleaching, or the formof rinse compositions to be applied before or after dyeing, bleaching,permanents, straightening, relaxing, waving or even between the twostages of a permanent or straightening process. The personalcare/cosmetic compositions may also take the form of skin-washingcompositions, and particularly in the form of solutions or gels for thebath or shower, or of make-up removal products. The personalcare/cosmetic compositions may also be in the form of aqueous orhydro-alcoholic solutions for skin and/or hair care. The personalcare/cosmetic compositions described herein are useful in personalcare/cosmetic products, including, but not limited to, gels, lotions,glazes, glues, mousses, sprays, fixatives, polymer based dyes (ref.WO2011/113249A1), shampoos, conditioners, 2-in-1 shampoos, temporaryhair dyes, semi-permanent hair dyes, permanent hair dyes, straighteners,permanent waves, relaxers, creams, putties, waxes, pomades,moisturizers, mascaras, lip balms and foam enhancers.

The modified polymers can be prepared according to the examples set outbelow. The examples are presented for purposes of demonstrating, but notlimiting, the preparation of the compounds and compositions of thisinvention.

EXAMPLES

The following non-limiting examples are provided to illustrate a few ofthe methods for preparing lactamic polymers containing an acetoacetatemoiety and functionalized lactamic polymers. The examples are presentedfor purposes of demonstrating, but not limiting, the preparation of thecompounds and compositions of this invention.

General Experimental

The terpolymer of poly(vinyl pyrrolidone-co-maleicanhydride-co-acetoacetoxyethyl methacrylate) (PVP/MAN/AAEM) basedmaterials were prepared as described in Hood, D. K.; Visscher, K. B.;Kamin, S., PCT/US2011/55701. Hydroxyethyl Cellulose (HEC) and polyvinylpyrrolidone (PVP) K-30 are available from Ashland Specialty Ingredients.Polyvinyl alcohol (PVOH) (88% hydrolyzed, Mw 13K to 23K) is availablefrom Aldrich, Milwaukee, Wis. Polyfunctional aziridine (PZ-33) isavailable from Polyaziridine, LLC. Glyoxal is available from TCIAmerica, Portland, Oreg. Dispal 11N7-80 (Al₂O₃) is available from SasolNorth America Inc, Houston, Tex. Hydroxyethyl acrylate (HEA), triethylamine (TEA), and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) are availablefrom Aldrich Chemicals. De-ionized water and ethanol were used.

A 10% by weight solution of PVP/MAN/AAEM was prepared by mixing 10 gramsof the polymer with 90 grams of 50:50 blend of de-ionized water andethanol (by weight). These mixtures were left to mix overnight on arotating wheel yielding clear solutions. A quantity of 10% by weightsolutions of HEC, PVOH, and PVP K30 were similarly prepared. Mixtures ofthese solutions were made to evaluate cross-linking potential. Coatingswere drawn on to 4 mil white Melinex®¹³ film with a #80 rod. Films werecured in an oven set at 140° C. for 30 minutes for PVOH containingcoatings. Films were cured in an oven set at 120° C. for 20 minutes forHEC containing coatings. Control coating films were dried at 130° C. for30 minutes.

Coatings of PVP/MAN/AAEM (in 50:50 ethanol:water) with 5 wt % ofglyoxal, 5 wt % PZ-33, and 5 wt % of 1:1 glyoxal:PZ-33 were prepared asabove in ethanol:water mixture. Coatings were drawn on to 4 mil whiteMelinex® film with a #80 rod. Films were cured at 130° C. for 30minutes.

Water resistance of the films was determined by immersing the curedfilms in de-ionized water with constant stirring. The coatings wereevaluated by rubbing the coating by hand to check coating removal.

The resulting wet film was placed into a Fusion UV LC-6B bench-topconveyor equipped with F300S/SQ lamp system. The belt speed was set for15 ft/min. The approximate dose is ˜1500 mJ/cm² and the intensity is 4.6W/cm². The printed film was allowed to stand for a minimum of 24 hours.

Gloss was measured at 60° using a BYK micro-TRI-gloss meter (Model 4430;Geretsried, Germany) when coating was applied to white Melanex® film.Pencils of various degrees of hardness were drawn over coated surface todetermine which pencil caused indentation. Harder surfaces requirehigher pencil numbers. Adhesion of coatings to clear Melinex® wasconducted by Cross-Hatch adhesion test with adhesive tape. For Taberabrasion, the coating was placed in a Teledyne 5150 Abraser (N.Tonawanda, N.Y.) equipped with CS-17 wheels and 1000 gram load. Solventresistance of the films was judged by MEK rub tests where a cheeseclothwas wrapped around a 16 oz ball hammer (300 g rub weight). The coatedsurface was rubbed for a maximum of 200 times while wetting thecheesecloth every 50 rubs. The coating was examined for signs of attacksuch as blistering, peeling, or discoloration.

Example 1 Synthesis of Vp/MAN/AcAc (33/33/33)

Feed one is prepared with 22.77 g vinyl pyrrolidone (Vp) and 39.41 gmethyl ethyl ketone (MEK, 2-butanone), 20.09 g maleic anhydride (MAN)and 43.90 g acetoacetoxyethyl methacrylate (AcAc). Put 189.15 g MEK intothe reactor and commence purging of the reaction vessel with nitrogen.Heat the reaction flask containing MEK to reflux at approximately 78° C.In a separate vessel, prepare a mixture of Triganox 25C 75 (15.0 g) andMEK (15 g). Label this vessel “Triganox Solution”. When the reactionflask has reached reflux temperature, begin adding Feed 1, drop-wise, into the reaction vessel over a period of 180 minutes. After 15 minutes ofmonomer feed, add 3 g of the Triganox Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately165 minutes. While the monomers are feeding into the reactor, after 30minutes charge 3.0 g of the Triganox solution. After 45, 60, 75, 90, 105and 120 minutes, charge 3.0 g Triganox solution into the reactor. After150 minutes, charge 3.0 g Triganox solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Triganox solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. During the initiatorshots, additional MEK was added to replace any that has volatilized.Cool the reaction vessel and leave the material in the reactor. This isthe end of day one. On day two, re-heat the vessel to reflux and chargewith 2.0 g Triganox 25C 75. Hold for 2 hours. Add an additional 2.0 gTriganox 25C 75. Hold for 5 hours then cool reaction mixture. Structureconfirmed by NMR. K-Value=9.3. Tg=96.4° C. (1st Heating)

Example 2 Synthesis of Vp/MAN-Sodium Salt/AcAc (33/33/33)

Samples of the polymer generated in Example 1 (Vp/MAN/AcAc (33/33/33)were precipitated into methyl t-butyl ether and dried to yield a(water-insoluble) white powder. One gram of the powder was suspended inwater (approx 50 g) and sodium bicarbonate powder is added to bring thepH of the water solution to pH 8. Additional bicarbonate is added tomaintain the pH at 8 as the polymer dissolves.

Example 3 Synthesis of Vp/MAN-Ammonium Hydroxide Salt/AcAc (33/33/33)

Samples of the polymer generated in Example 1 (Vp/MAN/AcAc (33/33/33)were precipitated into methyl t-butyl ether and dried to yield a (waterinsoluble) white powder. One gram of the powder was suspended in water(approx 50 g) and ammonium hydroxide solution is added to bring the pHof the water solution to pH 8. Additional ammonium hydroxide solution isadded to maintain the pH at 8 as the polymer dissolves.

Example 4 Synthesis of Vp/MAN/Iso-Octyl Acrylate/AcAc (33/33/31/2)

Feed one is prepared with 23.18 g vinyl pyrrolidone (Vp) and 40.11 gMEK, 20.45 g maleic anhydride (MAN); 35.75 g iso-Octyl Acrylate and 2.68g acetoacetoxyethyl methacrylate (AcAc). Put 192.53 g MEK into thereactor and commence purging of the reaction vessel with nitrogen. Heatthe reaction flask containing MEK to reflux, approximately 78° C. In aseparate vessel prepare a mixture of Triganox 25C 75 (15.0 g) and MEK(15 g). Label this vessel “Triganox Solution”. When the reaction flaskhas reached reflux temperature, begin adding Feed 1, drop-wise, in tothe reaction vessel over a period of 180 minutes. After 15 minutes ofmonomer feed, add 3 g of the Triganox Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately165 minutes. While the monomers are feeding into the reactor, after 30minutes charge 3.0 g of the Triganox solution. After 45, 60, 75, 90, 105and 120 minutes, charge 3.0 g Triganox solution into the reactor. After150 minutes, charge 3.0 g Triganox solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Triganox solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. During the initiatorshots, additional MEK was added to replace any that has volatilized.Cool the reaction vessel and leave the material in the reactor. This isthe end of day one. On day two, re-heat the vessel to reflux and chargewith 2.0 g Triganox 25C 75. Hold for 2 hours. Add an additional 2.0 gTriganox 25C 75. Hold for 5 hours then cool reaction mixture.K-Value=9.7.

Example 5 Synthesis of Vp/MAN/Iso-Octyl Acrylate/OctylAcrylate/Allyl-AcAc (33/33/16.6/14.4/2)

Feed one is prepared with 23.24 g vinyl pyrrolidone (Vp) and 40.21 gMEK, 20.51 g maleic anhydride (MAN); 19.20 g iso-Octyl Acrylate; 16.64 gOctyl Acrylate and 1.78 g Allyl Acetoacetate (Allyl-AcAc). Put 192.53 gMEK into the reactor and commence purging of the reaction vessel withnitrogen. Heat the reaction flask containing MEK to reflux,approximately 78° C. In a separate vessel prepare a mixture of Triganox25C 75 (15.0 g) and MEK (15 g). Label this vessel “Triganox Solution”.When the reaction flask has reached reflux temperature, begin addingFeed 1, drop-wise, in to the reaction vessel over a period of 180minutes. After 15 minutes of monomer feed, add 3 g of the TriganoxSolution into the reactor. Continue the drop-wise addition of Feed 1over a period of approximately 165 minutes. While the monomers arefeeding into the reactor, after 30 minutes charge 3.0 g of the Triganoxsolution. After 45, 60, 75, 90, 105 and 120 minutes, charge 3.0 gTriganox solution into the reactor. After 150 minutes, charge 3.0 gTriganox solution into the reactor. At the completion of the monomerfeeds, charge the reaction vessel with the remainder of the Triganoxsolution. The reaction vessel is allowed to heat at reflux for anadditional 180 minutes. During the initiator shots, additional MEK wasadded to replace any that has volatilized. Cool the reaction vessel andleave the material in the reactor. This is the end of day one. On daytwo, re-heat the vessel to reflux and charge with 2.0 g Triganox 25C 75.Hold for 2 hours. Add an additional 2.0 g Triganox 25C 75. Hold for 5hours then cool reaction mixture. K-Value=9.0.

Example 6 Synthesis of Vp/MAN/Iso-Octyl Acrylate/OctylAcrylate/Allyl-AcAc (33/33/16.6/14.4/2) to Sodium and Ammonium Salts

Samples of the polymer generated in Example 5 (VP/MAN/iso OA/OA/allylacac (33/33/16.6/14.4/2) were precipitated into methyl t-butyl ether anddried to yield a (water insoluble) white powder. One gram of the powderwas suspended in water (approx 50 g) and ammonium hydroxide solution isadded to bring the pH of the water solution to pH 8. Additional ammoniumhydroxide solution is added to maintain the pH at 8 as the polymerdissolves.

Example 7 Synthesis of VpNCap/AcAc (94/3/3)

Feed one is prepared with 364.17 g vinyl pyrrolidone (Vp); 14.56 Vinylcaprolactam (VCap); and 22.40 g acetoacetoxyethyl methacrylate (AcAc).Put 748.50 g of water and 320.77 g of isopropanol into the reactor andcommence purging of the reaction vessel with nitrogen. Adjust pH to 7with sodium bicarbonate. Heat the reaction flask containingwater/isopropanol mixture to approximately 75° C. Nitrogen is bubbledthrough the solution throughout the heat-up and the feeding of themonomer. In a separate vessel prepare a mixture of Triganox 121 (8 g)and isopropanol (20.12 g). Label this vessel “Initiator Solution”. Whenthe reaction flask has reached 75° C., begin adding Feed 1, drop-wise,in to the reaction vessel over a period of 180 minutes. After 15 minutesof monomer feed, add 6 g of the Triganox Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately165 minutes. While the monomers are feeding into the reactor, after 30minutes charge 6.0 g of the Triganox solution. After 60, and 120minutes, charge 6.0 g Triganox solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Triganox solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. Cool the reaction vesseland leave the material in the reactor. This is the end of day one. Onday two, re-heat the vessel to 75° C. and charge with 1.5 g Triganox121/4 g Isopropanol. Hold for 2 hours. Add an additional 1.5 g Triganox121/4 g Isopropanol. Hold for 5 hours then cool reaction mixture.Structure confirmed by NMR. K-Value=56.7. Tg=162.5° C. (1st Heating)

Example 8 Synthesis of VCap/Vp/AcAc (67.3/30.6/2.1)

Feed one is prepared with 28.93 g vinyl pyrrolidone (Vp); 34.12 gethanol; 79.69 g vinyl caprolactam (VCap) and 3.82 g acetoacetoxyethylmethacrylate (AcAc). Put 145.35 g of ethanol into the reactor andcommence purging of the reaction vessel with nitrogen. Heat the reactionflask to approximately 70° C. Nitrogen is bubbled through the solutionthroughout the heat-up and the feeding of the monomer. In a separatevessel prepare a mixture of Triganox 121 (2 g) Label this vessel“Initiator Solution”. When the reaction flask has reached 70° C., beginadding Feed 1, drop-wise, in to the reaction vessel over a period of 180minutes. Add 0.5 g of the initiator solution when the monomer feedbegins (this is Time=0). After 60, 120 and 180 minutes of monomer feed,add 0.5 g of the Initiator Solution into the reactor. After thecompletion of the monomer addition, dilute with 56.12 g ethanol. Heatthe reaction to 78° C. and hold for 120 minutes. After the 120 minuteshold, add 0.75 g Triganox 121 initiator. Hold the reaction at 78 for 90minutes. After the 90 minute hold, cool the reaction vessel and leavethe material in the reactor. This is the end of day one. On day two,reheat the vessel to 78° C. and charge with 0.75 g Triganox 121. Holdfor 8 hours then cool reaction mixture. Tg=˜176° C. (1st Heating)

Example 9 Synthesis of VP/MAN/ACAC Michael Addition with ICEMA to Water

VP/MAN/AcAc (33/33/33) (28.4% solids in MEK) [27.5 g solution] was mixedwith isocyanatoethyl methacrylate (ICEMA˜98% solids) [0.347 g], as a 50%mole ratio to the number of moles of AcAc in the Vp/MAN/AcAc. Themixture was stirred at 50° C. for 8 hours. The product was precipitatedfrom methyl t-butyl ether. The reaction product was confirmed by NMRspectroscopy.

Example 10 Synthesis of VP/VI/ACAC (48/48/4)

Feed one is prepared with 26.67 g vinyl pyrrolidone (VP); 22.59 g vinylimidazole; and 4.28 g acetoacetoxyethyl methacrylate (AcAc). Put 50.0 gof ethanol into the reactor and commence purging of the reaction vesselwith nitrogen. Heat the reaction flask containing water/ethanol mixtureto approximately ˜80° C. Nitrogen is bubbled through the solutionthroughout the heat-up and the feeding of the monomer. In a separatevessel prepare a mixture of Vazo-64 (0.5 g) and Ethanol (30 g). Labelthis vessel “Initiator Solution”. When the reaction flask has reached80° C., begin adding Feed 1, drop-wise, in to the reaction vessel over aperiod of 120 minutes. After 15 minutes of monomer feed, add 5 g of theInitiator Solution into the reactor. Continue the drop-wise addition ofFeed 1 over a period of approximately 105 minutes. While the monomersare feeding into the reactor, after 30 minutes charge 5.0 g of theInitiator Solution. After 60, and 90 minutes, charge 5.0 g InitiatorSolution into the reactor. At the completion of the monomer feeds,charge the reaction vessel with the remainder of the Initiator Solution.The reaction vessel is allowed to heat at reflux for an additional 180minutes. Cool the reaction vessel and leave the material in the reactor.This is the end of ‘day one’. On ‘day two’, re-heat the vessel to 80° C.and charge with 15.0 g of the Initiator Solution. Hold for 2 hours. Addan additional 15.0 g of the Initiator Solution. Hold for 5 hours thencool reaction mixture. Structure confirmed by NMR. K-Value is 42.3 andTg is 90.8° C.

Example 11 Synthesis of VP/MAN/PEA/Allyl AcAc to Water

Feed one is prepared with 22.96 g vinyl pyrrolidone (Vp) and 40.12 gMEK, 20.25 g maleic anhydride (MAN); 36.09 g phenoxyethyl acrylate(PEA); 2.67 g allyl acetoacetate (allyl acac). Put 192.59 g MEK into thereactor and commence purging of the reaction vessel with nitrogen. Heatthe reaction flask containing MEK to reflux ˜78° C. In a separate vesselprepare a mixture of Triganox 25C 75 (15.0 g) and MEK (15 g). Label thisvessel “Triganox Solution”. When the reaction flask has reached refluxtemperature, begin adding Feed 1, drop-wise, in to the reaction vesselover a period of 180 minutes. After 15 minutes of monomer feed, add 3 gof the Triganox Solution into the reactor. Continue the drop-wiseaddition of Feed 1 over a period of approximately 165 minutes. While themonomers are feeding into the reactor, after 30 minutes charge 3.0 g ofthe Triganox solution. After 45, 60, 75, 90, 105 and 120 minutes, charge3.0 g Triganox solution into the reactor. After 150 minutes, charge 3.0g Triganox solution into the reactor. At the completion of the monomerfeeds, charge the reaction vessel with the remainder of the Triganoxsolution. The reaction vessel is allowed to heat at reflux for anadditional 180 minutes. Note: during the initiator shots, additional MEKwas added to replace any that has volatilized. Cool the reaction vesseland leave the material in the reactor. This is the end of ‘day one’. On‘day two’, re-heat the vessel to reflux and charge with 2.0 g Triganox25C 75. Hold for 2 hours. Add an additional 2.0 g Triganox 25C 75. Holdfor 5 hours then cool reaction mixture. After the reaction has beencooled, the reaction mixture is added to methyl t-butyl ether toprecipitate the product as a white powder. This material is soluble inaqueous ammonium hydroxide as well as MEK. Tg=46.5° C. (2nd Heating)

Samples of the polymer generated were precipitated into methyl t-butylether and dried to yield a (water-insoluble) white powder. One gram ofthe powder was suspended in water (approx 50 g) and sodium hydroxidesolution is added to bring the pH of the water solution to pH 8.

Example 12 Synthesis of VP/VA/Allyl AcAc

Feed one is prepared with 51.04 g vinyl pyrrolidone (Vp) and 42.05 gMEK, 15.25 g VA (vinyl acetate); 2.80 g allyl acac (allyl acetoacetate).Put 201.85 g MEK into the reactor and commence purging of the reactionvessel with nitrogen. Heat the reaction flask containing MEK to reflux˜78° C. In a separate vessel prepare a mixture of Triganox 25C 75 (15.0g) and MEK (15 g). Label this vessel “Triganox Solution”. When thereaction flask has reached reflux temperature, begin adding Feed 1,drop-wise, in to the reaction vessel over a period of 180 minutes. After15 minutes of monomer feed, add 3 g of the Triganox Solution into thereactor. Continue the drop-wise addition of Feed 1 over a period ofapproximately 165 minutes. While the monomers are feeding into thereactor, after 30 minutes charge 3.0 g of the Triganox solution. After45, 60, 75, 90, 105 and 120 minutes, charge 3.0 g Triganox solution intothe reactor. After 150 minutes, charge 3.0 g Triganox solution into thereactor. At the completion of the monomer feeds, charge the reactionvessel with the remainder of the Triganox solution. The reaction vesselis allowed to heat at reflux for an additional 180 minutes. Note: duringthe initiator shots, additional MEK was added to replace any that hasvolatilized. Cool the reaction vessel and leave the material in thereactor. This is the end of ‘day one’. On ‘day two’, re-heat the vesselto reflux and charge with 2.0 g Triganox 25C 75. Hold for 2 hours. Addan additional 2.0 g Triganox 25C 75. Hold for 5 hours then cool reactionmixture. K-Value=8.3. Tg=44° C. (2nd Heating)

Example 13 Synthesis of VP/DMAPMA/AcAc (45/50/5)

Feed one is prepared with 36.15 g vinyl caprolactam (VCap) and 36.99 gMEK, 4.9 g 3-dimethylaminopropyl methacrylamide (DMAPMA) and 61.81 gacetoacetoxyethyl methacrylate (AcAc). Put 177.57 g MEK into the reactorand commence purging of the reaction vessel with nitrogen. Heat thereaction flask containing MEK to reflux ˜78° C. In a separate vesselprepare a mixture of Triganox 25C 75 (15.0 g) and MEK (15 g). Label thisvessel “Triganox Solution”. When the reaction flask has reached refluxtemperature, begin adding Feed 1, drop-wise, in to the reaction vesselover a period of 180 minutes. After 15 minutes of monomer feed, add 3 gof the Triganox Solution into the reactor. Continue the drop-wiseaddition of Feed 1 over a period of approximately 165 minutes. While themonomers are feeding into the reactor, after 30 minutes charge 3.0 g ofthe Triganox solution. After 45, 60, 75, 90, 105 and 120 minutes, charge3.0 g Triganox solution into the reactor. After 150 minutes, charge 3.0g Triganox solution into the reactor. At the completion of the monomerfeeds, charge the reaction vessel with the remainder of the Triganoxsolution. The reaction vessel is allowed to heat at reflux for anadditional 180 minutes. Note: during the initiator shots, additional MEKwas added to replace any that has volatilized. Cool the reaction vesseland leave the material in the reactor. This is the end of ‘day one’. On‘day two’, re-heat the vessel to reflux and charge with 2.0 g Triganox25C 75. Hold for 2 hours. Add an additional 2.0 g Triganox 25C 75. Holdfor 5 hours then cool reaction mixture. Tg=42° C. (2nd Heating)

Example 14 Synthesis of VCap/VA/Allyl AcAc

Feed one is prepared with 61.65 g vinyl caprolactam (VCap) and 40.56 gMEK, 14.71 g VA (vinyl acetate); 2.70 g allyl acac (allyl acetoacetate).Put 194.69 g MEK into the reactor and commence purging of the reactionvessel with nitrogen. Heat the reaction flask containing MEK to reflux˜78 C. In a separate vessel prepare a mixture of Triganox 25C 75 (15.0g) and MEK (15 g). Label this vessel “Triganox Solution”. When thereaction flask has reached reflux temperature, begin adding Feed 1,drop-wise, in to the reaction vessel over a period of 180 minutes. After15 minutes of monomer feed, add 3 g of the Triganox Solution into thereactor. Continue the drop-wise addition of Feed 1 over a period ofapproximately 165 minutes. While the monomers are feeding into thereactor, after 30 minutes charge 3.0 g of the Triganox solution. After45, 60, 75, 90, 105 and 120 minutes, charge 3.0 g Triganox solution intothe reactor. After 150 minutes, charge 3.0 g Triganox solution into thereactor. At the completion of the monomer feeds, charge the reactionvessel with the remainder of the Triganox solution. The reaction vesselis allowed to heat at reflux for an additional 180 minutes. Note: duringthe initiator shots, additional MEK was added to replace any that hasvolatilized. Cool the reaction vessel and leave the material in thereactor. This is the end of ‘day one’. On ‘day two’, re-heat the vesselto reflux and charge with 2.0 g Triganox 25C 75. Hold for 2 hours. Addan additional 2.0 g Triganox 25C 75. Hold for 5 hours then cool reactionmixture.

Example 15 Synthesis of VP/HEP-MA/AcAc (93/5/2)

Feed one is prepared with 67.24 g vinyl pyrrolidone (VP); 6.34 gpyrrolidonoethyl methacrylate (HEP-MA); and 2.78 g acetoacetoxyethylmethacrylate (AcAc). Put 198.3 g of water and 49.60 g ethanol into thereactor and commence purging of the reaction vessel with nitrogen. Heatthe reaction flask containing water/ethanol mixture to approximately˜75° C. Nitrogen is bubbled through the solution throughout the heat-upand the feeding of the monomer. In a separate vessel prepare a mixtureof Vazo-64 (2 g) and VP (5 g). Label this vessel “Initiator Solution”.When the reaction flask has reached 75 C, begin adding Feed 1,drop-wise, in to the reaction vessel over a period of 180 minutes. After15 minutes of monomer feed, add 1 g of the Initiator Solution into thereactor. Continue the drop-wise addition of Feed 1 over a period ofapproximately 165 minutes. While the monomers are feeding into thereactor, after 30 minutes charge 1.0 g of the Initiator Solution. After60, and 120 minutes, charge 1.0 g Initiator Solution into the reactor.At the completion of the monomer feeds, charge the reaction vessel withthe remainder of the Initiator Solution. The reaction vessel is allowedto heat at reflux for an additional 180 minutes. Cool the reactionvessel and leave the material in the reactor. This is the end of ‘dayone’. On ‘day two’, re-heat the vessel to 75° C. and charge with 2.0 gof the Initiator Solution. Hold for 2 hours. Add an additional 2.0 g ofthe Initiator Solution. Hold for 5 hours then cool reaction mixture.K-Value is 54.4 and Tg is 84.9° C.

Example 16 Synthesis of Vp/MAN/AcAc (33/33/33) Grafted with Propargylalcohol

Dissolve 8.0 g of Poly(VP/MAN/AcAc) (PACMAN) in 20 ml NMP and add thesolution to the reaction flask. Add 20 ml of Propargyl alcohol to thereaction flask and heat the reaction mixture to 80° C. with continuousstirring. Hold the reaction at 80° C. for 36 hours. At the end of 36hours cool the reaction to room temperature. After the reaction has beencooled, the reaction mixture is added to methyl t-butyl ether toprecipitate the product-yellow solid. This product is soluble in NMP andDMSO. Product structure was confirmed by Carbon and Proton NMR. GlassTransition Temperature (T_(g)) of the product is 49.52° C.

Example 17 Synthesis of Vp/MAN/AcAc (33/33/33) Grafted with HydroxylEthyl Acrylate

Dissolve 4.0 g of Poly(VP/MAN/AcAc from Example 1) in 20 ml NMP and addthe solution to the reaction flask. Add 5 ml of 2-hydroxyethyl acrylate(HEA) to the reaction flask and slowly heat the reaction mixture to 65°C. with continuous stirring. Hold the reaction at 65° C. for 50 hours.At the end of 50 hours cool the reaction to room temperature. After thereaction has been cooled, the reaction mixture is added to methylt-butyl ether to precipitate the product-white solid. This product issoluble in NMP and DMSO. Product structure was confirmed by Carbon andProton NMR. Glass Transition Temperature (T_(g)) of the product is45.36° C.

Example 18 Synthesis of VPy/VI/VP/AcAc (40/40/18/2)

Feed one is prepared with 20.01 g vinyl pyrrolidone (VP); 37.65.59 gvinyl imidazole; 42.06 g 4-vinyl pyridine; and 4.28 g acetoacetoxyethylmethacrylate (AcAc). Put 100.0 g of ethanol into the reactor andcommence purging of the reaction vessel with nitrogen. Heat the reactionflask containing water/ethanol mixture to approximately ˜80° C. Nitrogenis bubbled through the solution throughout the heat-up and the feedingof the monomer. In a separate vessel prepare a mixture of Vazo-64 (1.0g) and Ethanol (60 g). Label this vessel “Initiator Solution”. When thereaction flask has reached 80° C., begin adding Feed 1, drop-wise, in tothe reaction vessel over a period of 120 minutes. After 15 minutes ofmonomer feed, add 10 g of the Initiator Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately105 minutes. While the monomers are feeding into the reactor, after 30minutes charge 10.0 g of the Initiator Solution. After 60, and 90minutes, charge 10.0 g Initiator Solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Initiator Solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. Cool the reaction vesseland leave the material in the reactor. This is the end of ‘day one’. On‘day two’, re-heat the vessel to 80° C. and charge with 30.0 g of theInitiator Solution. Hold for 2 hours. Add an additional 30.0 g of theInitiator Solution. Hold for 5 hours then cool reaction mixture. K-Valueis 30.0 and Tg is 69.8° C.

Example 19 Synthesis of VPy/VI/VP/AcAc (40/40/18/2)

A clear straw colored solution of polymer was obtained by dissolving 10grams of the previous polymer (Example 20) in 100 grams of DI wateradjusted to pH˜6 with hydrochloric acid.

Example 20 Synthesis of VP/MAN/Allyl AcAc (33/33/33)

Feed one is prepared with 23.77 g vinyl pyrrolidone (VP) and 41.14 gMEK, 20.98 g MAN (maleic anhydride); 30.41 g allyl acetoacetate (allylacac). Put 197.48 g MEK into the reactor and commence purging of thereaction vessel with nitrogen. Heat the reaction flask containing MEK toreflux ˜78° C. In a separate vessel prepare a mixture of Triganox 25C 75(15.0 g) and MEK (15 g). Label this vessel “Triganox Solution”. When thereaction flask has reached reflux temperature, begin adding Feed 1,drop-wise, in to the reaction vessel over a period of 180 minutes. After15 minutes of monomer feed, add 3 g of the Triganox Solution into thereactor. Continue the drop-wise addition of Feed 1 over a period ofapproximately 165 minutes. While the monomers are feeding into thereactor, after 30 minutes charge 3.0 g of the Triganox solution. After45, 60, 75, 90, 105 and 120 minutes, charge 3.0 g Triganox solution intothe reactor. After 150 minutes, charge 3.0 g Triganox solution into thereactor. At the completion of the monomer feeds, charge the reactionvessel with the remainder of the Triganox solution. The reaction vesselis allowed to heat at reflux for an additional 180 minutes. Note: duringthe initiator shots, additional MEK was added to replace any that hasvolatilized. Cool the reaction vessel and leave the material in thereactor. This is the end of ‘day one’. On ‘day two’, re-heat the vesselto reflux and charge with 2.0 g Triganox 25C 75. Hold for 2 hours. Addan additional 2.0 g Triganox 25C 75. Hold for 5 hours then cool reactionmixture. After the reaction has been cooled, the reaction mixture isadded to methyl t-butyl ether to precipitate the product, a whitepowder. This material is soluble in aqueous ammonium hydroxide as wellas MEK. K-Value=10.4. Tg=42° C. (1st Heating)

Example 21 Synthesis of VP/VCap/Allyl AcAc (94/3/3)

Feed one is prepared with 366.01 g vinyl pyrrolidone (VP) and 14.63 gvinyl caprolactam (VCap). A quantity of 752.28 g of water and 322.39 gisopropanol are placed in the 2 L reaction vessel equipped with amechanical stirrer, thermocouple, nitrogen line and condenser. The pH ofthe solvent solution is adjusted with sodium bicarbonate to about pH 7.A quantity of 14.94 g of allyl acetoacetate (Allyl AcAc) is added to thesolvent mixture and the solvent/allyl AcAc mixture are heated to 78 Cunder a nitrogen purge. In a separate vessel prepare a mixture ofTriganox 121 (8.02 g) and isopropanol (20.22 g). Label this vessel“Triganox Solution”. When the reaction flask has reached refluxtemperature, begin adding Feed 1, drop-wise, in to the reaction vesselover a period of 180 minutes. After 15 minutes of monomer feed, add 6 gof the Triganox Solution into the reactor. Continue the drop-wiseaddition of Feed 1 over a period of approximately 165 minutes. While themonomers are feeding into the reactor, after 30 minutes charge 6.0 g ofthe Triganox solution. After 60 and 120 minutes, charge 6.0 g Triganoxsolution into the reactor. At the completion of the monomer feeds,charge the reaction vessel with the remainder of the Triganox solution.The reaction vessel is allowed to heat at reflux for an additional 180minutes. Note: during the initiator shots, additional isopropanol wasadded to replace any that has volatilized. Cool the reaction vessel andleave the material in the reactor. This is the end of ‘day one’. On ‘daytwo’, re-heat the vessel to reflux and charge with 1.52 g Triganox121/4.04 g isopropanol. Hold for 2 hours. Add an additional 21.52 gTriganox 121/4.04 g isopropanol. Hold for 5 hours then cool reactionmixture. K-Value=36.7.

Example 22 Synthesis of Vp/MAN/AcAc/TEVS (25/25/25/25)

Feed one is prepared with 17.04 g vinyl pyrrolidone (Vp) and 38.31 gMEK, 15.03 g maleic anhydride (MAN); 29.12 g triethoxyvinyl silane(TEVS); 32.83 g Acetoacetoxyethyl methacrylate (acac). Put 183.94 g MEKinto the reactor and commence purging of the reaction vessel withnitrogen. Heat the reaction flask containing MEK to reflux 78° C. In aseparate vessel prepare a mixture of Triganox 25C 75 (15.0 g) and MEK(15 g). Label this vessel “Triganox Solution”. When the reaction flaskhas reached reflux temperature, begin adding Feed 1, drop-wise, in tothe reaction vessel over a period of 180 minutes. After 15 minutes ofmonomer feed, add 3 g of the Triganox Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately165 minutes. While the monomers are feeding into the reactor, after 30minutes charge 3.0 g of the Triganox solution. After 45, 60, 75, 90, 105and 120 minutes, charge 3.0 g Triganox solution into the reactor. After150 minutes, charge 3.0 g Triganox solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Triganox solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. Note: during the initiatorshots, additional MEK was added to replace any that has volatilized.Cool the reaction vessel and leave the material in the reactor. This isthe end of ‘day one’. On ‘day two’, re-heat the vessel to reflux andcharge with 2.0 g Triganox 25C 75. Hold for 2 hours. Add an additional2.0 g Triganox 25C 75. Hold for 5 hours then cool reaction mixture.After the reaction has been cooled, the reaction mixture is added tomethyl t-butyl ether to precipitate the product, a white powder. Thismaterial is soluble in aqueous ammonium hydroxide as well as MEK.Structure confirmed by NMR. K-Value=7.9. Tg=70° C. (1st Heating)

Samples of the polymer generated in Example above (Vp/MAN/AcAc/TEVS(25/25/25/25)) were precipitated into methyl t-butyl ether and dried toyield a (water insoluble) material. One gram of the material wassuspended in water (approx 50 g) and ammonium hydroxide solution isadded to bring the pH of the water solution to pH 8. Additional ammoniumhydroxide solution is added to maintain the pH at 8 as the polymerdissolves.

Example 23 Synthesis of Vp/MAN/GMA/Allyl AcAc (33/33/29/4)

Feed one is prepared with 23.59 g vinyl pyrrolidone (Vp) and 41.23 gMEK, 20.81 g maleic anhydride (MAN); 27.43 g glycidyl methacrylate(GMA); 2.74 g allyl acetoacetate (allyl acac). Put 192.59 g MEK into thereactor and commence purging of the reaction vessel with nitrogen. Heatthe reaction flask containing MEK to reflux ˜78° C. In a separate vesselprepare a mixture of Triganox 25C 75 (15.0 g) and MEK (15 g). Label thisvessel “Triganox Solution”. When the reaction flask has reached refluxtemperature, begin adding Feed 1, drop-wise, in to the reaction vesselover a period of 180 minutes. After 15 minutes of monomer feed, add 3 gof the Triganox Solution into the reactor. Continue the drop-wiseaddition of Feed 1 over a period of approximately 165 minutes. While themonomers are feeding into the reactor, after 30 minutes charge 3.0 g ofthe Triganox solution. After 45, 60, 75, 90, 105 and 120 minutes, charge3.0 g Triganox solution into the reactor. After 150 minutes, charge 3.0g Triganox solution into the reactor. At the completion of the monomerfeeds, charge the reaction vessel with the remainder of the Triganoxsolution. The reaction vessel is allowed to heat at reflux for anadditional 180 minutes. Note: during the initiator shots, additional MEKwas added to replace any that has volatilized. Cool the reaction vesseland leave the material in the reactor. This is the end of ‘day one’. On‘day two’, re-heat the vessel to reflux and charge with 2.0 g Triganox25C 75. Hold for 2 hours. Add an additional 2.0 g Triganox 25C 75. Holdfor 5 hours then cool reaction mixture. After the reaction has beencooled, the reaction mixture is added to methyl t-butyl ether toprecipitate the product—a white powder. This material is partiallysoluble in aqueous ammonium hydroxide. Tg=48° C. (2nd Heating)

Example 24 Cementing Compound

To a beaker containing 21 grams of DI water, 0.09 grams of Xanthan gum(XG 200, from ISP) was added with high shear mixing followed by 0.3grams of cellulose gum (Aquapac, from Hercules). 0.45 grams of Tween80(ICI) and 15.2 grams of Barium sulfate (Berifine BF21 from Cimbar)were mixed into the above composition.

grams of VP/MAN/AcAC solution (3 grams polymer in 7 grams of ethanol and2 grams of water) was then mixed into the above composition. 14.25 gramsof 30 wt % Polyethyleneimine (Aldrich) was added with constant mixingand the mixture was let set overnight at room temperature.

Example 25 Preparation of Microcapsules Cross-Linked with VP/MAN/AcAc

In an 8 dram vial place 1.0 g VP/VA/GMA dissolved in3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbonate; 1.0 g Xtend 226and a small amount of water insoluble indigo pigment. Add 3 drops ofDETA (diethylene tetramine) and stir to incorporate it into the mixture.Add ‘one drop’ of ViviPrint 300 and stir to incorporate into themixture.

Prepare a solution containing 150 mL water and 6.0 g VP/MAN/AcAc-NH4OHsolution. Add 0.5 g DBN to the VP/MAN/AcAc solution. Add the VP/VA/GMAmixture drop-wise to the aqueous, vigorously stirring VP/MAN/AcAcsolution. The blue VP/VA/GMA mixture should break into small beads withstirring. Remove the initial water, add additional water to wash thebeads and neutralize the solution. Samples of the blue beads were placedin solutions of pure water and also acetone to check for stability. Inboth cases, the beads remain intact.

Example 26 Synthesis of HEP-MA/MAN/AcAc

Feed one is prepared with 46.1 g hydroxyethylpyrrolidone methacrylate(HEP-MA) and 45.06 g MEK, 22.97 g maleic anhydride (MAN); 50.19 gAcetoacetoxyethyl methacrylate (acac). Put 146 g MEK into the reactorand commence purging of the reaction vessel with nitrogen. Heat thereaction flask containing MEK to reflux ˜78° C. In a separate vesselprepare a mixture of Triganox 25C 75 (15.0 g) and MEK (15 g). Label thisvessel “Triganox Solution”. When the reaction flask has reached refluxtemperature, begin adding Feed 1, drop-wise, in to the reaction vesselover a period of 180 minutes. After 15 minutes of monomer feed, add 3 gof the Triganox Solution into the reactor. Continue the drop-wiseaddition of Feed 1 over a period of approximately 165 minutes. While themonomers are feeding into the reactor, after 30 minutes charge 3.0 g ofthe Triganox solution. After 45, 60, 75, 90, 105 and 120 minutes, charge3.0 g Triganox solution into the reactor. After 150 minutes, charge 3.0g Triganox solution into the reactor. At the completion of the monomerfeeds, charge the reaction vessel with the remainder of the Triganoxsolution. The reaction vessel is allowed to heat at reflux for anadditional 180 minutes. Note: during the initiator shots, additional MEKwas added to replace any that has volatilized. Cool the reaction vesseland leave the material in the reactor. This is the end of ‘day one’. On‘day two’, re-heat the vessel to reflux and charge with 2.0 g Triganox25C 75. Hold for 2 hours. Add an additional 2.0 g Triganox 25C 75. Holdfor 5 hours then cool reaction mixture. This material is soluble inaqueous ammonium hydroxide as well as MEK. The structure was confirmedby NMR. Tg=39° C. (1st Heating)

Example 27 Synthesis of HEP-MA/MAN/AcAc to Ammonium Salts

Samples of the polymer generated in Example above (HEP-MA/MAN/AcAc(33/33/33)) were precipitated into methyl t-butyl ether and dried toyield a (water insoluble) material. One gram of the material wassuspended in water (approx 50 g) and ammonium hydroxide solution isadded to bring the pH of the water solution to pH 8. Additional ammoniumhydroxide solution is added to maintain the pH at 8 as the polymerdissolves.

Example 28 Synthesis of Butyl Acrylate Block on VpNCap/AcAc (94/3/3)

30 g of Vp/VCap/AcAc (94/3/3) (0.0042 moles AcAc is contained in thepolymer) was dissolved in approximately 90 g of isopropanol.Phenoxyethyl acrylate (PEA) (0.90 g; 0.0042 moles) and DBN base (0.03 g)are added to the Vp/VCap/AcAc isopropanol mixture and it is stirred atroom temperature overnight. A molar excess of n-butyl acrylate (nBA) (4g; 0.032 moles) is added to the reaction mixture and the reaction isheated to reflux for 8 hours. The mixture is cooled, and precipitatedfrom methyl t-butyl ether to yield a white solid. Structure wasconfirmed by NMR.

Example 29 Solubility of 5% by Weight Polymer at Room Temperature

Solubility VP/MAN/ PEA/VP/MAN/ VP/MAN/AcAc - Solvent AcAc AllylAcAcICEMA 2-HEA ✓ ✓ ✓ 2-HBA ✓ ✓ X GPTA/SR9020 X X X HDDA/SR238B X X XPEA/SR340 X X X THFA/SR285 X ✓ X EOTMPTA/SR454 X X X Di-TMPTA/SR355 X XX TMPTA/SR351LV X X X EGDMA X X X DEGDMA/SR231 X X X HDBOHPBA X X X(partially soluble over 2 Wks) PETA/aldrich X X X Epoxycyclo hexyl X X Xmethyl methacrylate Methyl oxetane ✓ ✓ ✓ methanol Heloxy 68 X X X Cycloepoxy* X X X Cas#2386-87-0 Ethanol X X X IPA X X X Ethanol:Water 50:50 ✓X X IPA:Water 50:50 ✓ X X Water-pH > 7 ✓ ✓ ✓

+1,6-Hexanediylbisloxy(2-hydroxy-3,1-propanediyl)] bisacrylate

*3,4-epoxy cyclohexyl methyl 3,4-epoxy cyclo hexane carboxylate

Example 30 Synthesis of Vp/MAN/PEA/AcAc (33/33/25/8)

Feed one is prepared with 23.24 g vinyl pyrrolidone (Vp) and 40.62 gMEK, 20.50 g maleic anhydride (MAN); 25.76 g phenoxyethyl acrylate(PEA); 9.19 g allyl Acetoacetoxyethyl methacrylate (AcAc). Put 194.95 gMEK into the reactor and commence purging of the reaction vessel withnitrogen. Heat the reaction flask containing MEK to reflux ˜78° C. In aseparate vessel prepare a mixture of Triganox 25C 75 (15.0 g) and MEK(15 g). Label this vessel “Triganox Solution”. When the reaction flaskhas reached reflux temperature, begin adding Feed 1, drop-wise, in tothe reaction vessel over a period of 180 minutes. After 15 minutes ofmonomer feed, add 3 g of the Triganox Solution into the reactor.Continue the drop-wise addition of Feed 1 over a period of approximately165 minutes. While the monomers are feeding into the reactor, after 30minutes charge 3.0 g of the Triganox solution. After 45, 60, 75, 90, 105and 120 minutes, charge 3.0 g Triganox solution into the reactor. After150 minutes, charge 3.0 g Triganox solution into the reactor. At thecompletion of the monomer feeds, charge the reaction vessel with theremainder of the Triganox solution. The reaction vessel is allowed toheat at reflux for an additional 180 minutes. Note: during the initiatorshots, additional MEK was added to replace any that has volatilized.Cool the reaction vessel and leave the material in the reactor. This isthe end of ‘day one’. On ‘day two’, re-heat the vessel to reflux andcharge with 2.0 g Triganox 25C 75. Hold for 2 hours. Add an additional2.0 g Triganox 25C 75. Hold for 5 hours then cool reaction mixture.After the reaction has been cooled, the reaction mixture is added tomethyl t-butyl ether to precipitate the product, a white powder. Thismaterial is soluble in aqueous ammonium hydroxide as well as MEK.K-Value=7.1

Example 31 Synthesis of Vp/MAN/AcAc/TEGMEM (25/25/25/25)

Feed one is prepared with 16.73 g vinyl pyrrolidone (Vp) and 37.62 gMEK, 14.76 g maleic anhydride (MAN); 34.96 g triethyleneglycol methylether methacrylate (TEGMEM); 32.24 g Acetoacetoxyethyl methacrylate(acac). Put 183.94 g MEK into the reactor and commence purging of thereaction vessel with nitrogen. Heat the reaction flask containing MEK toreflux—approximately ˜78° C. In a separate vessel prepare a mixture ofTriganox 25C 75 (15.0 g) and MEK (15 g). Label this vessel “TriganoxSolution”. When the reaction flask has reached reflux temperature, beginadding Feed 1, drop-wise, in to the reaction vessel over a period of 180minutes. After 15 minutes of monomer feed, add 3 g of the TriganoxSolution into the reactor. Continue the drop-wise addition of Feed 1over a period of approximately 165 minutes. While the monomers arefeeding into the reactor, after 30 minutes charge 3.0 g of the Triganoxsolution. After 45, 60, 75, 90, 105 and 120 minutes, charge 3.0 gTriganox solution into the reactor. After 150 minutes, charge 3.0 gTriganox solution into the reactor. At the completion of the monomerfeeds, charge the reaction vessel with the remainder of the Triganoxsolution. The reaction vessel is allowed to heat at reflux for anadditional 180 minutes. Note: during the initiator shots, additional MEKwas added to replace any that has volatilized. Cool the reaction vesseland leave the material in the reactor. This is the end of ‘day one’. On‘day two’, re-heat the vessel to reflux and charge with 2.0 g Triganox25C 75. Hold for 2 hours. Add an additional 2.0 g Triganox 25C 75. Holdfor 5 hours then cool reaction mixture. This material is soluble inaqueous ammonium hydroxide as well as MEK. K-Value=8.3.

Example 32 Membrane Premix

To a N-methyl-2-pyrrolidone (NMP) is added VP/VCap/Allyl AcAc (94/3/3)(74:26 parts). Optional ingredients include polysulfones, PVDF, andsimilar useful high performance thermoplastics as outlined inWO/2010/111607.

The polymers of the invention are suitable for use in industrial,personal care, household, and pharmaceutical applications. Industrialuses include, but are not limited to, formulating inks (U.S. Pat. App.Ser. No. 61/293,834 and 61/263,570, the contents of which are herebyincorporated by reference), flocculation agents, hydrogels, surfacemodification agents, coatings, microporous print media, shale swellinhibitors, metal coatings, metal working fluids, rheology modifiers,reactive biocides, decorated titanium, diazo functionalmaterials/pigments, interlaminate adhesives, dispersants, batteries,products comprised of iodine, products comprised of silver, productscomprised of carbon, products comprised of nano carbons, comb/branchpolymer adducts, biocidal films, tackifiers, polymeric dyes, latexweather resistant modifiers, decorated pigments for inks and pastes,decorated cenospheres, decorated barium sulfate, surface decorated PVPPparticles, cross-linkers (see U.S. patent application Ser. No.12/698,583, the contents of which are hereby incorporated by reference),automotive products and protective films, super-absorbers (i.e.,diapers) (see U.S. Pat. App. 2009/0043005A1, the contents of which arehereby incorporated by reference), printing plates, macro-initiatingmaterials, products comprised of graphene, hydrophilic enhancementagents for membranes (see U.S. Pat. App. Ser. No. 61/242,900 andPCT/2010/028852, the contents of which are hereby incorporated byreference), anti-fog coatings, polymer blocks, additives to extrudablecompounds and films, protective colloidal agents, multi dimensionalprinting pigments and inks (for example see WO/2008/077850A2, thecontents of which are hereby incorporated by reference), refractiveindex modifiers, cross-linking agents, rheology control agents, greaseresistant films, fiber sizing agents, products comprised of alumina,conductive films, cementitious compositions, bioadhesives, tabletcoatings, battery binders, resinous photo-initiators (see U.S. patentapplication Ser. No. 12/698,583, the contents of which are herebyincorporated by reference), resinous UV absorbers (U.S. patentapplication Ser. No. 12/698,583, the contents of which are herebyincorporated by reference), iodine stabilizers, conductive coatings andgels, reactive rheology modifying agents, macro-initiators, coating flexagents, and non-migratory anti-static agents. Personal care andhousehold applications include, but are not limited to, formulatingcosmetics, hair care products, toiletries, hydrogels, laundry productsand household cleaning products, dye absorbent non-woven swatches, metalchelators (i.e., Ca, Mg, etc. . . . ) Pharmaceutical applicationsinclude, but are not limited to, processing aids, medical stents,catheters and other medical device coatings, active ingredientsolubilizers, optical lenses, formulating drug delivery systems, andpreparing tablet coatings.

Results and Discussion

The poly(vinyl pyrrolidone-co-maleic anhydride-co-acetoacetoxyethylmethacrylate) (PVP/MAN/AAEM) terpolymer has a number of interestingfeatures. First, the maleic anhydride form of the terpolymer iscompatible with ketone based solvents. When introduced to water, themaleic anhydride can hydrolyze to form the vicinal maleic acidterpolymer, which can be suitably neutralized with ammonium hydroxide orother bases, such as sodium hydroxide as set out below (ProposedStructures of PVP/MAN/AAEM and PVP/MAA/AAEM Curable polymers)

Another interesting facet of the PVP/MAN/AAEM terpolymer is the stronghydrogen bonding capacity of the pyrrolidonyl carbonyl group coupled tothe proton donating group on the maleic group yielding zwitterionicbehavior, Subotic, D., Ferguson, J., Warren, B. C. H., European PolymerJournal, Vol. 25, Number 12, pp. 1233-1237 (1989). The physicalproperties of the PVP/MAN/AAEM polymer are presented in the Table below.In general, the polymer is a low viscosity material that exhibits areasonably high T_(g). In addition to the previously mentionedproperties, the polymer also exhibits high gloss, transparency, filmforming, and dye fixation properties.

Property PVP/MAN/AAEM Data Viscosity (cPs) (50% in HEA) 1,580 (DV-III,100 RPM, #4 Spindle) T_(g) (° C.) ~95 (1^(st) Heating) K-Value range ~10

HEC+PVP/MAN/AAEM and PVOH+PVP/MAN/AAEM Films

In printing applications, both cellulosics and polyvinyl alcohols areimportant binders and film forming technologies. Previous work haddemonstrated the effectiveness of combining cellulosic and polyvinyllactam binders to enhance the absorption of applied printing ink,Nadeau, L. N., Waddell, W., Hood, D. K., Johnson, E., Kitchen, J. P.,Sarkar, M. M., Evans, D. L., Gratton, R., US 2006/0134363 A1. A varietyof films have been made to elucidate the cross-linking potential ofPVP/MAN/AAEM by employing an established thermal esterification betweenthe maleic acid and hydroxyl functionalities. This cross-linkingapproach is presented schematically below. (Proposed Structure forCross-linked PVP/MAN/AAEM with Polyvinyl Alcohol)

Such approaches are known for similar materials like Gantrez,poly(maleic anhydride-co-methyl vinyl ether), “Gantrez AN Copolymer,”ISP Product Brochure 2302-128R, 1995. Coating compositions andobservation of film performance are presented in the Table below.(Thermally cured coating compositions and observations)

Brookfield Viscosity Coating Mix (DVIII+) (cPs, 100 Composition Ratio PHRPM, RT)) Observation PVP K-30 + HEC 1:1 6 260 Minor water resistancePVP/MAN/AAEM + 1:1 3 176 Excellent water HEC resistance PVP K-30 + PVOH1:1 7 17 No water resistance PVP/MAN/AAEM + 1:1 3 20 Excellent waterPVOH resistance PVP K-30 1 6 17 No water resistance PVP/MAN/AAEM 1 2 8No water resistance HEC 1 6 2000 No water resistance PVOH 1 7 42 Nowater resistance

Both the cured films of PVP/MAN/AAEM+HEC and PVP/MAN/AAEM+PVOH exhibitexcellent water resistance, as compared to their non-reactive PVPcounterparts. The PVP/MAN/AAEM+HEC coating also exhibited excellentwater resistance. These films were clear and glossy, exhibiting 60°gloss values >85. Pencil hardness was determined to be 8H. Cross-cutadhesion to white Melinex® film for neat polymer films and their blendswas excellent. The exception was PVP/MAN/AAEM+HEC, where coatingexhibited ˜90% removal. All of the polymer coatings exhibited goodsolvent resistance. There was no blistering, peeling, or discoloration.The noted exception was PVP/MAN/AAEM and PVP/MAN/AAEM+HEC coatings,where discoloration was observed after ˜100 rubs.

PVP/MAN/AAEM+A1₂O₃ Films

In micro-porous printing applications, alumina pigments are criticalcomponents to the print receptive layer, U.S. Pat. No. 4,474,847. A keyfeature of the micro-porous coating pigment loading is that the drycoating comprises ˜90% (by weight) pigment. A common binder employed inthese coatings is PVOH, which can cross-link with melamine/formaldehyde,glyoxal, or zirconates. For the PVP/MAN/AAEM terpolymer, AAEM monomeralso known as good chelator of metals such as copper and alumina. Avariety of films were made to elucidate the cross-linking potential ofPVP/MAN/AAEM employing alumina chelation and thermal esterificationprinciple to the coating approach as set out below. (PVP/MAN/AAEM+A1₂O₃:film compositions and observations)

Coating (wt % ratio) Mix Ratio PH Observation PVP/MAN/AAEM + 3:7 2 WaterDispal 11N7-80 Resistant PVOH + Dispal 11N7-80 3:7 2 Water ResistantPVP/MAN/AAEM + PVOH + 1.5:1.5:7 2 Water Dispal 11N7-80 Resistant

PVP/MAN/AAEM+Glyoxal+Aziridine, Thermal Dual Cure

Work on polymers comprising carboxylic acid and aceto acetyl moietiesfor dual cure coatings demonstrated that using a cross-linker blend ofdialdehyde-aziridine enabled improvements to water resistance ofnon-woven articles, such as paper towels, Goldstein, J. E., Pangrazi, R.J., U.S. Pat. No. 6,117,492. An interesting feature of this curingapproach, is the low temperature cure range (20° C.-40° C.). Utilizingthis approach, we evaluated the cure response of PVP/MAN/AAEM. Both hightemperature and ambient temperature curing were evaluated as set outbelow. (PVP/MAN/AAEM+Glyoxal+Aziridine: film compositions andobservations)

Cure Coating Composition Mix Ratio Temperature ObservationPVP/MAN/AAEM + Glyoxal + 10:1:3 30° C. Water Aziridine for 20 hoursResistant PVP/MAN/AAEM + Glyoxal + 10:1:3 140° C. Water Aziridine for 30min Resistant

Excellent water resistance was observed for both high temperature andlow temperature curing. Note that for low temperature, the time wasextended to enable the coating to dry.

PVP/MAN/AAEM+HEA+DBN+Aziridine, UV-Thermal Dual Cure

To render this oligomer suitable for UV cross-linking, the base oligomerwas acrylated by employing “Michael Addition” of the oligomer to theacrylate with the base catalyst DBN. Such approaches have beenthoroughly presented in earlier papers, Mathur, B. D.; Viswanathan, K.;Miller, K. M.; Long, T. E., Prog. Polym. Sci., Vol. 31, pp. 487-531(2006), Gould, M. L.; Narayan-Sarathy, S.; Hammond, T. E.; Fechter, R.B., RadTech Europe (2005). Mechanistically, addition of DBN enables thedeprotonation of the acetoacetoxy's methylene group to yield an enolateanion. The enolate anion then readily attacks, in the fashion of1,4-conjugate addition, the olefin of the acrylate. The carbonylstabilizes the resulting anion until the base is regenerated from protontransfer. This reaction occurs easily at room temperature. The result isan oligomer suitable for further initiating common UV coating monomerand oligomer components. For dual cure, aziridine was also added toenable facile, low temperature reactive cross-linking with the acidgroups of maleic anhydride. A schematic of these proposed reactions ispresented below. (proposed mechanism of dual cure of PVP/MAN/AAEM viathe Michael Addition and aziridine

Various non-aqueous coating compositions were made to demonstrate thedual cure functionality of this system. The coatings are presented inthe Table below. (Compositions for PVP/MAN/AAEM UV-Thermal dual cure)

Material Coating I Coating II Coating III Coating IV PVP/MAN/AAEM 48.7548.75 47.25 46 HEA 48.75 48.75 47.25 46 Darocur 1173 2.5 — — — DBN — 2.52.5 2.4 TEA — — 0.5 — PZ-33 (aziridine) — — 2.5 5.6 Total 100 100 100100

The Table below presents the final physical coating properties.

Property Coating I Coating II Coating III Coating IV AppearanceTransparent Transparent Transparent Hazy Gloss High High High HighPencil 2H 2H 3H 6H Hardness Adhesion 100% 100% 100% 100% MEK Rubs 60 100180 >200 Water Water Water Water Water Resistance Resistant ResistantResistant Resistant

PVP/MAN/AAEM in HEA exhibited UV cure in presence of photo initiator.Interestingly, PVP/MAN/AAEM exhibited cure, in the absence ofphoto-initiator, where only the Michael Addition product formed by DBNwas employed. Films were glossy, transparent and exhibited excellentadhesion. PVP/MAN/AAEM exhibited dual cure (UV and thermal) in presenceof DBN and aziridine. This is demonstrated by the boost in theperformance of the film, comparing DBN to DBN+aziridine. The additionalaziridine boosts the MEK rub resistance, which is indicative of a newcure response for the coating system.

While a number of embodiments of this invention have been represented,it was apparent that the basic construction can be altered to provideother embodiments that utilize the invention without departing from thespirit and scope of the invention. All such modifications and variationsare intended to be included within the scope of the invention as definedin the appended claims rather than the specific embodiments that havebeen presented by way of example.

1. A lactamic polymer comprising an acetoacetate moiety having thefollowing structure:

wherein each R₁ is independently selected from the group consisting ofhydrogen and C₁-C₃₀ functionalized and unfunctionalized alkyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₃ is independently selectedfrom the group consisting of hydrogen and C₁-C₆ functionalized andunfunctionalized alkyl, amide, carbonyl, and carboxyl groups, whereinany of the before mentioned groups may be with or without heteroatoms,and mixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; w, x, and y are molepercent, the sum of which=100%; and each n is an integer independentlyranging from 1-4.
 2. The polymer according to claim 1, wherein each R₁is independently hydrogen or methyl.
 3. The polymer according to claim1, wherein each R₃ is —C(O)OCH₂CH₂—.
 4. (canceled)
 5. The polymeraccording to claim 1, wherein each R₅ is independently selected from thegroup consisting of C₁-C₈ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof.
 6. The polymer accordingto claim 1, wherein w ranges from 1-97%, x ranges from 1-97%, and yranges from 1-97%.
 7. The polymer according to claim 1, wherein each nis an integer independently ranging from 1-3.
 8. The polymer accordingto claim 1, wherein the polymer has a structure selected from the groupconsisting of:

9-16. (canceled)
 17. A composition comprising a lactamic polymercontaining an acetoacetate moiety having the following structure:wherein each R₁ is independently selected from the group consisting ofhydrogen and C₁-C₃₀ functionalized and unfunctionalized alkyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₃ is independently selectedfrom the group consisting of hydrogen and C₁-C₆ functionalized andunfunctionalized alkyl, amide, carbonyl, and carboxyl groups, whereinany of the before mentioned groups may be with or without heteroatoms,and mixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; w, x, and y are molepercent, the sum of which=100%; and each n is an integer independentlyranging from 1-4.
 18. The composition according to claim 17, whereineach R1 is independently hydrogen or methyl.
 19. The compositionaccording to claim 17, wherein each R₃ is —C(O)OCH₂CH₂—.
 20. (canceled)21. The composition according to claim 17, wherein each R₅ isindependently selected from the group consisting of C₁-C₈ functionalizedand unfunctionalized alkyl and alkenyl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof.
 22. The composition according to claim 17, wherein w rangesfrom 1-97%, x ranges from 1-97%, and y ranges from 1-97%.
 23. Thecomposition according to claim 17, wherein each n is an integerindependently ranging from 1-3.
 24. The composition according to claim17, wherein the polymer has a structure selected from the groupconsisting of:

25-36. (canceled)
 37. The composition according to claim 17, wherein thecomposition comprises adhesives, aerosols, agricultural compositions,anti-soil redeposition agents, batteries, beverages, biocides, blockcopolymers, branch/comb copolymers, cementing compositions, cleaningcompositions, coating compositions, conductive materials, cosmeticcompositions, cross-linkers, dental compositions, polymeric dyes,decorated pigments, detergents, dispersants, drugs, electronics,encapsulations, foods, hair sprays, household-industrial-institutional,inks and coatings, interlaminate adhesives, lithographic solutions,membrane additive compositions, metal working fluids, oilfieldcompositions, paints, paper, personal care compositions,pharmaceuticals, pigment additives, plasters, plastics, printing,reactive biocides, refractive index modifiers, sequestrants, soilrelease compositions, static control agents, and wood-care compositions.38-40. (canceled)
 41. The polymer according to claim 1, wherein thepolymer is in an inert solvent.
 42. (canceled)
 43. The polymer accordingto claim 1, wherein the polymer is in powder form with a Tg>80° C. 44.The polymer according to claim 43, wherein the polymer is in powder formwith a Tg>95° C. 45-46. (canceled)
 47. The polymer according to claim 1,wherein the polymer is in a reactive solvent.
 48. (canceled)
 49. Thepolymer according to claim 1, wherein the polymer is in a liquidcross-linker. 50-52. (canceled)